CN100486003C - Nonaqueous electrolyte battery - Google Patents
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- CN100486003C CN100486003C CNB2005800010214A CN200580001021A CN100486003C CN 100486003 C CN100486003 C CN 100486003C CN B2005800010214 A CNB2005800010214 A CN B2005800010214A CN 200580001021 A CN200580001021 A CN 200580001021A CN 100486003 C CN100486003 C CN 100486003C
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Abstract
The invention provides a nonaqueous electrolyte battery, which is provided with a positive electrode (1) containing lithium iron phosphate as a positive electrode active material, a negative electrode (2), and a nonaqueous electrolyte (4). In the positive electrode (1), a positive electrode mixture layer composed of a positive electrode active material, a conductive agent and a binder is formed on a positive electrode current collector, the thickness of the positive electrode current collector is less than 20 [ mu ] m, and the average surface roughness (Ra) of the surface in contact with the positive electrode mixture layer exceeds 0.026 [ mu ] m. According to the present invention, even when olivine-type lithium phosphate is used as the positive electrode active material, the adhesion between the positive electrode active material and the positive electrode current collector can be improved, and the volume energy density and the load characteristics can be improved.
Description
Technical field
The present invention relates to a kind of possessed as positive active material contain positive pole, the negative pole of LiFePO4, the nonaqueous electrolyte battery of nonaqueous electrolyte, particularly improved improvement with the positive electrode collector of the connecting airtight property of positive active material.
Background technology
In recent years, the miniaturization and of personal digital assistant devices such as portable phone, PC, PDA develops by leaps and bounds, for as the further high capacity of the battery request of its driving power.With the lithium rechargeable battery is the rechargeable nonaqueous electrolytic battery of representative owing to have high-energy-density, the capacity height, and the driving power that therefore is used as aforesaid personal digital assistant device extensively utilizes.
Described rechargeable nonaqueous electrolytic battery as a rule uses by cobalt acid lithium (LiCoO
2) wait positive pole that the lithium-containing transition metal composite oxides constitute, maybe can inhale negative pole that material with carbon elements such as graphite that storage discharges lithium constitute, in ethylene carbonate (EC) or diethyl carbonate organic solvents such as (DEC), dissolve by boron lithium fluoride (LiBF by lithium metal or lithium alloy
4) or phosphorus hexafluoride acid lithium (LiPF
6) the electrolytical nonaqueous electrolyte that waits lithium salts to constitute.In this kind battery, be accompanied by and discharge and recharge, lithium ion moves between positive and negative electrode, thereby discharges and recharges.
But, in the battery that has used cobalt acid lithium as positive electrode,, be expensive material because cobalt is the resource of the limited rareness of storage, therefore can cause using the rising of production cost of its battery.In addition, in the battery that has used cobalt acid lithium, under charged state, think and make the electrolyte burning because oxygen in the positive pole is released when being difficult to be in the high temperature of the degree under the common user mode therefore also have the problem of thermal stability reduction when reaching.Thus, as the positive electrode that replaces cobalt acid lithium, studying LiMn2O4 (LiMn
2O
4) or lithium nickelate (LiNiO
2) utilization that waits.But, under the situation of having used described LiMn2O4, can't expect enough discharge capacities, and when battery temperature uprises, manganese is dissolved in the electrolyte and separates out the problem that has cycle characteristics to reduce on negative pole.On the other hand, under the situation of having used lithium nickelate, problems such as discharge voltage reduction are arranged.
Consider this kind situation, in recent years, olivine-type lithium phosphates such as LiFePO4 are used as the positive electrode that replaces cobalt acid lithium and receive publicity.This olivine-type lithium phosphate is with general formula Li
xM
1-(d+t+q+r)D
dT
tQ
qR
r(XO
4) (M=Fe, Mn, Co, Ti, Ni's is at least a, and X=Si, S, P, V's is at least a, selects D=Mg in the ion of D by divalent
2+, Ni
2+, Co
2+, Zn
2+, Cu
2+, select T=Al in the ion of T by 3 valencys
3+, Ti
3+, Cr
3+, Fe
3+, Mn
3+, Ga
3+, Zn
3+, V
3+, select Q=Ti in the ion of Q by 4 valencys
4+, Ge
4+, Sn
4+, V
4+, select R=V in the ion of R by 5 valencys
5+, Nb
5+, Ta
5+, 0 ≦ x ≦ 1,0 ≦ d, t, q, r ≦ 1) and the lithium complex chemical compound of expression, according to the kind difference of the metallic element M that becomes core and operation voltage is different.
Thus, have, just can at random set the advantage of cell voltage by suitably being selected to the metallic element M of core.In addition, because theoretical capacity also reaches the higher degree of ratio about 140mAh/g～170mAh/g, therefore the advantage of the battery capacity that can increase per unit mass is arranged.In addition, at the LiFePO4 (LiFePO that has selected iron as the M in the general formula
4) in, have the advantage that can reduce the production cost of battery significantly because of using many, the cheap iron of quantum of output.
But, when the positive active material that the olivine-type lithium phosphate is used as nonaqueous electrolyte battery uses, the problem that should solve being arranged still, particularly following situation becomes very big problem.That is, removing of the lithium the during battery charging and discharging of olivine-type lithium phosphate inserted reaction slowly, in addition with described cobalt acid lithium or lithium nickelate or LiMn2O4 (LiMn
2O
4) wait and compare, electron conduction is very low.Thus, used the particularly polarization increase when high rate discharge of battery of olivine-type lithium phosphate, the problem that has battery behavior to worsen significantly.
In order to address this problem, in following patent documentation 1, use LiFePO has been proposed
4The particle diameter of one-level particle reach the method for the following very little degree of 3.1 μ m, positive active material that specific area is enough big.
Though by using the positive active material that is proposed in this patent documentation 1, increase with the contact area of conductive agent, the electron conduction of positive active material is good, yet owing to use the very little positive active material of particle diameter, therefore there is the packed density of positive active material to reduce, the problem that also reduces as cell integrated energy density.In addition, the olivine-type lithium phosphate is low with connecting airtight property as the metal forming of positive electrode collector, even hybrid adhesive also has the problem of peeling off from positive electrode collector easily.Up to now, in following patent documentation 2, propose,, suppress the method for peeling off from the positive electrode collector of positive active material by in the big positive electrode collector of surface roughness, anode mixture being set.
Patent documentation 1: the spy opens communique 2002-No. 110162
Patent documentation 2: the spy opens flat 5-No. 6766 communiques
But, be used as the LiCoO that positive active material uses in the past
2, LiNiO
2, Li
xNi
1- yCo
yO
2, LiMn
2O
4And LiNi
1/3Co
1/3Mn
1/3O
2Deng because good aspect the connecting airtight property, therefore not only under the situation of having used positive electrode collector with the surface roughness described in the patent documentation 2, and under the situation of having used the positive electrode collector that does not have the surface roughness described in the patent documentation 2, also the positive active material of q.s can be disposed on the positive electrode collector.In contrast, because the olivine-type lithium phosphate is low with connecting airtight property as the metal forming of positive electrode collector, even therefore hybrid adhesive also has the problem of peeling off from positive electrode collector.
In such cases, though can consider reduced thickness with the anode mixture layer, suppress the method that positive active material is peeled off from positive electrode collector, but when the time with the reduced thickness of anode mixture layer, positive electrode collector shared ratio in anodal whole thickness improves, thereby the problem that reduces as anodal volume energy density is arranged.In addition, because olivine-type lithium phosphate and employed LiCoO in the past
2, LiNiO
2, Li
xNi
1-yCo
yO
2, LiMn
2O
4And LiNi
1/3Co
1/3Mn
1/3O
2Resistance is bigger Deng comparing, and therefore under situation about discharging and recharging with big electric current, the voltage of battery reduces, thereby the problem that can't obtain enough charge/discharge capacities is arranged.
In order to address this problem,, can't say enough ideals though carried out improving researchs such as conductivity at the surface-coated carbon of olivine-type lithium phosphate.In addition, when for positive active material is peeled off from positive electrode collector, and when after the coating of anode mixture, rolling fully, then not only volume energy density reduces, and the contact area of positive active material, conductive agent, positive electrode collector tails off, thereby becomes the reason that causes load characteristic to reduce.
Summary of the invention
So, the present invention finishes in view of aforesaid problem, its purpose is, following nonaqueous electrolyte battery is provided, that is, under the situation of olivine-type lithium phosphate as positive active material that will constitute, can not reduce energy density as battery by LiFePO4 etc., and make anodal electron conduction that the raising of certain degree be arranged, thereby the acquisition capacity is high and the nonaqueous electrolyte battery of the discharge performance can increase substantially high rate discharge the time.
In order to reach described purpose, the invention of technical scheme 1 is the nonaqueous electrolyte battery that has possessed the positive pole that formed the positive active material that contains the olivine-type lithium phosphate as positive active material and contain layer on positive electrode collector, negative pole, nonaqueous electrolyte, it is characterized in that, the thickness of described positive electrode collector is less than 20 μ m, and contains the average surface roughness Ra of the face that layer contact above 0.026 μ m with described positive active material.
As mentioned above, be used as the employed LiCoO of positive active material in the past
2, LiNiO
2, Li
xNi
1 -yCo
yO
2, LiMn
2O
4And LiNi
1/3Co
1/3Mn
1/3O
2The electron conduction and the LiFePO of positive active material self
4Compare highlyer, the connecting airtight property separately of positive active material and conductive agent, conductive agent and positive electrode collector, positive electrode collector and positive active material can not become big problem.Thus, using these positive active materials (LiCoO
2, LiNiO
2, Li
xNi
1-yCo
yO
2, LiMn
2O
4And LiNi
1/3Co
1/3Mn
1/3O
2) positive pole in, charge-discharge characteristic can not change a lot because of the size with positive active material contains the average surface roughness Ra (the following average surface roughness Ra that abbreviates positive electrode collector sometimes as) of the face that contacts of layer of positive electrode collector.
But because the electron conduction of the positive active material self of olivine-type lithium phosphate is low, so the connecting airtight property separately of positive active material and conductive agent, conductive agent and positive electrode collector, positive electrode collector and positive active material becomes big problem.Thus, when with the olivine-type lithium phosphate during as positive active material, the average surface roughness Ra of positive electrode collector is big more, then demonstrates to be more particularly to demonstrate good charge-discharge characteristic by good charge-discharge characteristic when high speed.Particularly, if the average surface roughness Ra of positive electrode collector surpasses 0.026 μ m, then can demonstrate very good charge-discharge characteristic when high rate discharge (particularly flash-over characteristic).This be because, if the average surface roughness Ra of positive electrode collector surpasses 0.026 μ m, the then contact area of positive electrode collector and anode mixture layer increase, the connecting airtight property of positive active material particle and positive electrode collector improves widely, contact resistance diminishes.
In addition, if the connecting airtight property of positive active material particle and positive electrode collector improves widely, even then the mode that increases according to the thickness that makes the anode mixture layer forms the anode mixture layer on positive electrode collector, also can prevent anode mixture layer peeling off from the positive electrode collector.Consequently, owing to can keep the state that positive electrode collector has kept the anode mixture layer, therefore just can the LiCoO that positive active material uses will be used as in the past
2Such capacity is partly coated on the positive electrode collector of the same area.
In addition, because of the connecting airtight property raising of anode mixture layer and positive electrode collector, just can suppress anode mixture layer that the calendering by positive pole causes peeling off from the positive electrode collector.Thus, just can roll fully, can improve volume energy density, and the contact area of positive active material and conductive agent also increases, therefore make anodal whole conductivity further improve, load characteristic also improves.
And when the thickness of positive electrode collector became big, positive electrode collector shared volume in positive pole increased relatively, and anodal volume energy density reduces.So shown in constituting as described, the thickness of positive electrode collector is preferably set to less than 20 μ m, more preferably is set at below the 15 μ m.
And, LiFePO4 (LiFePO
4) wait so-called olivine-type lithium phosphate to be meant, with general formula Li
xM
1 -(d+t+q+r)D
dT
tQ
qR
r(XO
4) (M=Fe, Mn, Co, Ti, Ni's is at least a, and X=Si, S, P, V's is at least a, selects D=Mg in the ion of D by divalent
2+, Ni
2+, Co
2 +, Zn
2+, Cu
2+, select T=Al in the ion of T by 3 valencys
3+, Ti
3+, Cr
3+, Fe
3+, Mn
3+, Ga
3+, Zn
3+, V
3+, select Q=Ti in the ion of Q by 4 valencys
4+, Ge
4+, Sn
4+, V
4+, select R=V in the ion of R by 5 valencys
5+, Nb
5+, Ta
5+, 0 ≦ x ≦ 1,0 ≦ d, t, q, r ≦ 1) expression the compound with olivine-type crystal structure.
Representational example is LiFePO
4, LiCoPO
4Deng, Li for example
0.90Ti
0.05Nb
0.05Fe
0.30Co
0.30Mn
0.30PO
4Deng also suitable with it.Particularly, though LiFePO
4Obtaining of the iron compound that becomes raw material be easy to, yet having used under the situations such as Co, Ni as other transition metal, Mn, also be particle with identical crystal structure, therefore can expect identical effect.
In addition, the application's surface roughness Ra is formulated (with reference to following explanation) by JIS (JIS B 0601-1994), for example can utilize the surface roughness meter to measure.
The definition of surface roughness Ra
As shown in Figure 1, when the direction along its average line from roughness curve extracts datum length L, get in the direction of the average line of this extraction part and to make X-axis, get in the direction of vertical multiplying power and to make Y-axis, when roughness curve is represented with y=f (x), be meant the amount that to utilize the several 1 following value of trying to achieve with micron (μ m) expression.And among Fig. 1, m is a datum line.
And positive active material is not limited to the independent material of olivine-type lithium phosphate. also can be the mixture of olivine-type lithium phosphate and other positive electrode.
Technical scheme 2 described inventions are to have following feature in technical scheme 1 described invention,, use LiFePO4 as described olivine-type lithium phosphate that is.
Shown in constituting as described, if use LiFePO4 as the olivine-type lithium phosphate, then the quantum of output because of iron is many, cheap, thereby has the advantage that can reduce the production cost of battery significantly.
Technical scheme 3 described inventions are to have following feature in technical scheme 1 described invention,, use aluminium foil in described positive electrode collector, and described average surface roughness Ra are less than 0.20 μ m that is.
In addition, technical scheme 4 described inventions are to have following feature in technical scheme 2 described inventions,, use aluminium foil in described positive electrode collector, and described average surface roughness Ra are less than 0.20 μ m that is.
As shown in technical scheme 1,, need reduce the thickness of positive electrode collector in order to prevent the reduction of anodal volume energy density.On the other hand, when the thickness that reduces positive electrode collector, and when increasing average surface roughness Ra (μ m), then can produce the problem that the intensity of positive electrode collector reduces.
Here, used in positive electrode collector under the situation of aluminium foil, tensile strength is at 160N/mm
2More than, preferred 170N/mm
2More than.In addition, if the thickness that will use aluminium foil obtains described hot strength less than the positive electrode collector of 20 μ m, according to experimental verification, preferably the average surface roughness Ra with positive electrode collector is set at less than 0.20 μ m.
That is, used in positive electrode collector under the situation of aluminium foil, the average surface roughness Ra of positive electrode collector is preferably below 1/100 of thickness of positive electrode collector.But, this result adopts the situation of the grinding making positive electrode collector that uses sand-blast (blast method), in the method that adopts in addition, for example under the situation that etching method, coating method etc. are handled, also the average surface roughness Ra of positive electrode collector can be set at big (for example the thickness of positive electrode collector is about below 1/50) a little.The reason of She Dinging is like this, under the situation of the grinding of having used sand-blast, because it is big to the impact of positive electrode collector, therefore when increasing the average surface roughness Ra of positive electrode collector, then the intensity of positive electrode collector reduces, on the other hand, under the situation of using etching method, coating method etc. to handle, since little to the impact of positive electrode collector, even therefore increase the average surface roughness Ra of positive electrode collector to a certain extent, also can prevent the reduction of the intensity of positive electrode collector.
Technical scheme 5 described inventions are to have following feature in technical scheme 3 described inventions, that is, described asperities processing is to utilize the grinding of sand-blast to carry out.
Technical scheme 6 described inventions are to have following feature in technical scheme 4 described inventions, that is, described asperities processing is to utilize the grinding of sand-blast to carry out,
Set like this and be based on reason as follows promptly, positive electrode collector is being carried out under the situation of asperities processing, consider from the viewpoint of the reduction of the intensity that prevents positive electrode collector, preferred aforesaid etching method, the coating method etc. of using, yet the operation of these methods is very miscellaneous, and manufacturing cost raises.In contrast, under the situation that adopts the grinding of using sand-blast, operation is not miscellaneous, can reduce manufacturing cost.
Technical scheme 7 described inventions are to have following feature in technical scheme 2 described inventions, that is, the average grain diameter of described LiFePO4 is below 10 μ m.
By setting the average grain diameter of positive active material like this, just can control the diffusion length that is accompanied by the lithium that discharges and recharges generation in the positive active material particle, have and reduce the resistance that the insertion that is accompanied by lithium breaks away from generation, improve the effect of charge-discharge characteristic.That is, aspect the contact area that can guarantee active material particle and positive electrode collector by the control roughness fully, if use the LiFePO4 (LiFePO that has controlled particle diameter
4) then more effective.And, the median particle diameter (R of the positive active material particle diameter of measuring with laser diffraction formula particle size distribution device preferably
Median) and maximum frequency particle diameter (R
Mode) preferably all below 10 μ m, the particle that preferred 5 μ m are following.
Technical scheme 8 described inventions are to have following feature in technical scheme 1 described invention, that is, contain at described positive active material and to contain conductive agent in the layer, and the BET specific area of this conductive agent is set to 15m
2More than/the g, and described positive active material contain the layer packed density be set to 1.7g/cm
3More than.
In addition, technical scheme 9 described inventions are to have following feature in technical scheme 2 described inventions, that is, contain at described positive active material and to contain conductive agent in the layer, and the BET specific area of this conductive agent is set to 15m
2More than/the g, and described positive active material contain the layer packed density be set to 1.7g/cm
3More than.
In addition, technical scheme 10 described inventions are to have following feature in technical scheme 4 described inventions, that is, contain at described positive active material and to contain conductive agent in the layer, and the BET specific area of this conductive agent is set to 15m
2More than/the g, and described positive active material contain the layer packed density be set to 1.7g/cm
3More than.
If as described formation, the BET specific area of conductive agent is set at 15m
2More than/the g, the packed density that positive active material is contained layer is set at 1.7g/cm
3More than, even then in positive active material, contain olivine-type lithium phosphates such as LiFePO4, also can not reduce anodal energy density ground and improve electron conduction widely, therefore just can realize high capacity, and the discharge performance can significantly improve high rate discharge the time.This is considered to be caused by reason as follows
That is, the inventor confirms carrying out further investigation back, in the BET of conductive agent specific area less than 15m
2Under the situation of/g, the contact area of positive active material and conductive agent diminishes, and in addition, contains the packed density of layer less than 1.7g/cm at positive active material
3Situation under, anodal energy density reduces, and the connecting airtight property reduction of positive active material and conductive agent and positive active material and positive electrode collector.Because these results, when the BET of conductive agent specific area or positive active material contain the packed density hour of layer, then anodal energy density reduces, and the electron conduction in anodal becomes insufficient, can't realize high capacity, and the discharge performance during high rate discharge reduces.
In contrast, when as described formation, the BET specific area of conductive agent is set at 15m
2When/g is above, then the particle diameter owing to conductive agent diminishes, the conductive agent that can on the surface of positive active material, disperse q.s, so the contact area of positive active material and conductive agent increases, and be set at 1.7g/cm when the packed density that positive active material is contained layer
3When above, then can not reduce the connecting airtight property that anodal energy density ground improves positive active material and conductive agent and positive active material and positive electrode collector.Because these results, when the packed density that the BET specific area of conductive agent or positive electrode material is contained layer is set as described above, then can not reduce anodal energy density, and in anodal formation favorable conductive passage, electron conduction in anodal improves significantly, therefore can realize the high capacity of battery, and the discharge performance can improve high rate discharge significantly the time.
And, as electroconductive powder, preferably use conductive carbon powders, yet also can use metal oxide with conductivity etc.In addition, when the addition of electroconductive powder is too much, then because the mixed proportion of positive active material relatively reduces, and anodal charge/discharge capacity diminishes, thus the addition of electroconductive powder preferably with respect to the quality of anode mixture integral body below 10 quality %.
Technical scheme 11 described inventions are to have following feature in technical scheme 8 described inventions, that is, the packed density that described positive active material contains layer is set to 3.15g/cm
3Below.
Technical scheme 12 described inventions are to have following feature in technical scheme 9 described inventions, that is, the packed density that described positive active material contains layer is set to 3.15g/cm
3Below.
Set like this and be based on following reason, that is, the packed density that contains layer when positive active material surpasses 3.15g/cm
3The time, then anodal interior space becomes too small, and the quantitative change of the electrolyte that floods in electrode is few, thereby the situation of the discharge capacity reduction of battery is arranged.
According to described explanation, the packed density that positive active material contains layer is preferably set to 1.7g/cm
3Above 3.15g/cm
3Below, yet in this scope, be preferably set to 1.7g/cm
3Above 2.7g/cm
3Below, be preferably set to 2.0g/cm especially
3Above 2.3g/cm
3Below.
Technical scheme 13 described inventions are to have following feature in technical scheme 1 described invention,, apply or be attached with carbon on the surface of described positive active material particle that is.
The electron conduction of olivine-type lithium phosphates such as LiFePO4 is low to be a problem, and specifically, the conductivity with cobalt acid lithium of bedded rock salt tectonic is about 10
-3More than the S/cm, and as a kind of LiFePO4 (LiFePO of olivine-type lithium phosphate
4) conductivity be about 10
-10S/cm.So, if as described formation, on the surface of positive active material particle, apply or adhere to carbon, then can expect further to improve the effect of the conductivity in anodal.
Technical scheme 14 described inventions are to have following feature in technical scheme 1 described invention, that is, the part at the lithium position of described positive active material is replaced by transition metal.
As described formation, the part at the lithium position of positive active material is replaced with transition metal, then also can expect to improve the effect of the conductivity in anodal.
In order to reach described purpose, technical scheme 15 described inventions are to have possessed to have formed on the positive electrode collector surface to contain the positive active material that comprises the olivine-type lithium phosphate and the positive active material of conductive agent contains the positive pole of layer, the negative pole that contains the negative electrode active material that can inhale storage, release lithium, the nonaqueous electrolyte battery of nonaqueous electrolyte, it is characterized in that the BET specific area of described conductive agent is set to 15m
2More than/the g, and described positive active material contain the layer packed density be set to 1.7g/cm
3More than.
If be described formation, then can bring into play and the identical effect of technical scheme 8～10 described effects.
Technical scheme 16 described inventions are to have following feature in technical scheme 15 described inventions,, use LiFePO4 as described olivine-type lithium phosphate that is.
If be described formation, then can bring into play and the identical effect of technical scheme 2 described effects.
Technical scheme 17 described inventions are to have following feature in technical scheme 15 described inventions, that is, the packed density that described positive active material contains layer is set to 3.15g/cm
3Below.
In addition, technical scheme 18 described inventions are to have following feature in technical scheme 16 described inventions, that is, the packed density that described positive active material contains layer is set to 3.15g/cm
3Below.
If described 2 formations then can be brought into play and technical scheme 11 and the identical effect of 12 described effects.
According to the present invention, because under the prerequisite that does not reduce anodal energy density, in anodal, form the favorable conductive passage, electron conduction in anodal improves significantly, therefore play following effect, that is, can realize the high capacity of battery, and the discharge performance can improve high rate discharge significantly the time.
Description of drawings
Fig. 1 is the key diagram that is used to illustrate surface roughness Ra.
Fig. 2 is used to illustrate maximum height R
MaxKey diagram.
Fig. 3 is the figure that schematically shows the Experimental cell that has used positive pole of the present invention.
Wherein, 1: positive pole, 2: negative pole, 4: nonaqueous electrolyte
Embodiment
To be described as follows best mode of the present invention below, but the present invention is not subjected to any qualification of this mode, in the scope that does not change purpose of the present invention, can suitably changes and implement.
[anodal making]
At first, according to the average grain diameter (median particle diameter (R that makes as positive active material
Median) and maximum frequency particle diameter (R
Mode) both sides) be the LiFePO4 (LiFePO of 3 μ m
4) reach positive active material contain 85 a whole quality % of layer, make acetylene black as conductive agent (electrochemical industry system, DENKABLACK) reach a mode that positive active material contains 10 whole quality % of layer and measure after, both are mixed.Then, in this mixture, add polyacrylonitrile (PAN), make it to reach positive active material and contain 5 a whole quality % of layer, add N-methyl pyrrolidone (NMP) solution in addition in right amount as solvent as binding agent, by mixing manufacture slip.
On the other hand, to have prepared to utilize surface roughness Ra be 0.18 μ m (Ra=0.18 μ m), by the maximum height R of definition regulation described later
MaxBe 2.2 μ m (R
Max=2.2 μ m), thickness be 19.4 μ m enforcement the positive electrode collector made of the aluminium foil of asperities blasting treatment.Then, the two sides that the skill in using a kitchen knife in cookery is coated positive electrode collector is scraped in the slip utilization of having made.Then, use electric hot tray, make the NMP volatilization 80 ℃ of dryings.After the drying, cut the size of 2cm * 2cm, use cylinder with given thickness (under this situation, the thickness of the single face of anode mixture layer is 60 μ m), calendering is for reaching given active material packed density (being 2.2g/ml under this situation), then by it has been made anodal 1 100 ℃ of following vacuumizes.
The definition of maximum height Ry
As shown in Figure 2, be meant from roughness curve along the direction of its average line and extract datum length L, should extract the ummit line of part and the interval (R of valley line along the direction detection of the vertical multiplying power of roughness curve
P+ R
V), will be worth amount with micron (μ m) expression.And among Fig. 2, m is a datum line.
[making of negative pole]
By the size of lithium metallic plate with 3cm * 2.5cm cut, made negative pole 2.
[modulation of nonaqueous electrolyte]
By in the electrolyte with the volume ratio mixing of 1:1 with ethylene carbonate and diethyl carbonate, dissolving is as the LiPF of lithium salts
6, make it to reach 1 mol, modulated nonaqueous electrolyte 4.
[making of Experimental cell]
As shown in Figure 3, under inert atmosphere, will as the effect utmost point described anodal 1, be disposed in the Experimental cell container 6 every the barrier film (highpore of Asahi Kasei Corporation's system) 5 of polyethylene system as negative pole 2 folders the utmost point, by in Experimental cell container 6, injecting described nonaqueous electrolyte 4, made Experimental cell.And among Fig. 3,3 is metal with reference to the utmost point by lithium.
Embodiment
[the 1st embodiment]
(embodiment)
As embodiment, positive pole and Experimental cell have been made in the same manner with the best mode that is used to implement described invention.
Below, positive pole and the Experimental cell of so making is called anodal a of the present invention and battery A of the present invention respectively.
(comparative example 1)
Except having used by the surface roughness Ra of not implementing the asperities blasting treatment is 0.026 μ m (Ra=0.026 μ m), maximum height R
MaxBe 0.59 μ m (R
Max=0.59 μ m), thickness is beyond the positive electrode collector made of the aluminium foil of 15 μ m, to have made positive pole and Experimental cell in the same manner with embodiment.
Below, positive pole and the Experimental cell of so making is called anodal x1 of comparison and comparison battery X1 respectively.
(comparative example 2)
Except having used by surface roughness Ra is 0.28 μ m (Ra=0.28 μ m), maximum height R
MaxBe 4.4 μ m (R
Max=4.4 μ m), thickness be 30 μ m enforcement beyond the positive electrode collector made of the aluminium foil of asperities processing, made positive pole and Experimental cell in the same manner with embodiment.
Below, positive pole and the Experimental cell of so making is called anodal x2 of comparison and comparison battery X2 respectively.
(experiment 1)
Use described battery A of the present invention and comparison battery X1,2, investigated discharging current and be the discharge capacity (mAh/g) of the every 1g active material under the situation of 0.1It, 0.2It, 0.5It, 1.0It and 2.0It, these results are shown in the table 1.And the condition that discharges and recharges is as follows.
[condition that discharges and recharges when discharging current is 0.1It]
Charge condition
Charging current for charging to cell voltage with 0.1It reaches 4.5V.
Discharging condition
Be discharged to cell voltage with the discharging current of 0.1It and reach 2.0V.
Discharge and recharge the discharge capacity (mAh/g) when discharging under the described conditions by the 0.1It that has tried to achieve every 1g active material the discharge time of 1 circulation time.
[condition that discharges and recharges when discharging current is 0.2It]
When described discharging current is 0.1It discharge and recharge end after, under following condition, discharge and recharge.
Charge condition
Charging current for charging to cell voltage with 0.2It reaches 4.5V.
Discharging condition
Be discharged to cell voltage with the discharging current of 0.2It and reach 2.0V.
To discharge and recharge under the described conditions carried out 2,3,4,5,6 circulations repeatedly after, by the discharge capacity (mAh/g) in 0.2It when discharge of having tried to achieve every 1g active material the discharge time of 6 circulation times.
[condition that discharges and recharges when discharging current is 0.5It]
When described discharging current is 0.2It discharge and recharge end after, under following condition, discharge and recharge.
Charge condition
Charging current for charging to cell voltage with 0.2It reaches 4.5V.
Discharging condition
Be discharged to cell voltage with the discharging current of 0.5It and reach 2.0V.
Discharge capacity (mAh/g) when discharging by the 0.5It that has tried to achieve every 1g active material the discharge time of 7 circulation times.
[condition that discharges and recharges when discharging current is 1.0It]
When described discharging current is 0.5It discharge and recharge end after, under following condition, discharge and recharge.
Charge condition
Charging current for charging to cell voltage with 0.2It reaches 4.5V.
Discharging condition
Be discharged to cell voltage with the discharging current of 1.0It and reach 2.0V.
Discharge capacity (mAh/g) when discharging by the 1.0It that has tried to achieve every 1g active material the discharge time of 8 circulation times.
[condition that discharges and recharges when discharging current is 2.0It]
When described discharging current is 1.0It discharge and recharge end after, under following condition, discharge and recharge.
Charge condition
Charging current for charging to cell voltage with 0.2It reaches 4.5V.
Discharging condition
Be discharged to cell voltage with the discharging current of 2.0It and reach 2.0V.
Discharge capacity (mAh/g) when discharging by the 2.0It that has tried to achieve every 1g active material the discharge time of 9 circulation times.
And, the result of the average discharge volt when having tried to achieve the 2.0It discharge, battery A of the present invention is 2.8V, and relatively battery X1 is 2.6V, and relatively battery X2 is 2.8V.
[table 1]
Can be clear that from the result of described table 1 in the comparison battery X1 that has possessed the anodal x1 of comparison that uses the positive electrode collector of being made by the aluminium foil of not implementing the asperities blasting treatment, be accompanied by high rate discharge, the discharge capacity of every 1g active material reduces.In contrast, in the battery A of the present invention, the comparison battery X2 that have possessed the anodal a of the present invention who uses the positive electrode collector of making by the aluminium foil of having implemented the asperities blasting treatment, the anodal x2 of comparison, compare with comparing battery X1, be accompanied by high rate discharge, the discharge capacity of every 1g active material improves.This be because, in the anodal a of the present invention who has used the positive electrode collector of making by the aluminium foil of having implemented the asperities processing, the anodal x2 of comparison, becoming the aluminium foil of positive electrode collector and the contact area of anode mixture layer increases, contact resistance reduces, therefore the utilance of active material improves, and the discharge capacity of every 1g active material increases.
(experiment 2)
Based on the result of described experiment 1, calculated the volume capacity density of the anodal a of the present invention and comparison anodal x1, x2 based on following (3) formula, its result is shown in the table 2.
The discharge capacity of volume capacity density (mAh/ml)=every 1g positive active material * (quality of the quality/anode mixture of positive active material) * (packed density of active material) * (thickness that the thickness of anode mixture layer/positive pole is whole) ... (3)
Here, for example when the 1.0It of the anodal a of the present invention discharge, the discharge capacity of every 1g positive active material is 124.7 (mAh/g), the quality of the quality/anode mixture of positive active material=90/10, the packed density of active material is 2.2g/ml, the thickness of the thickness of anode mixture layer/positive pole integral body=(60+60)/(60+60+19.4).By with these numerical value substitutions described (3) formula, then the volume capacity density during the 1.0It discharge of the anodal a of the present invention is 212.5mAh/ml.
[table 2]
Can be clear that from the result of described table 2, in the comparison battery X2 that possesses the anodal x2 of comparison that has used the positive electrode collector of making by the aluminium foil of having implemented the asperities blasting treatment, when 1.0It discharges, compare with the comparison battery X2 that possesses the anodal x1 of comparison that has used the positive electrode collector of being made by the aluminium foil of not implementing the asperities blasting treatment, volume energy density reduces.In addition, in the battery A of the present invention that possesses the anodal a of the present invention that has used the positive electrode collector of making by the aluminium foil of having implemented the asperities blasting treatment, X1 compares with Experimental cell, and when 1.0It discharges and under 2.0It when discharge two kinds of situations, volume energy density all improves.
This is because in more anodal x2, owing to the thickness of the asperities aluminium foil that becomes positive electrode collector is thicker, reach 30 μ m, so positive electrode collector shared volume in positive pole increases anodal volume energy density reduction.Thus, become positive electrode collector the asperities aluminium foil thickness as the anodal a of the present invention less than 20 μ m.Under this situation, though need the average surface roughness Ra of control thickness less than the aluminium foil of 20 μ m, use sand-blast to make average surface roughness Ra is the aluminium foil of 0.20 μ m, also can be created in the technical situation that is difficult to realize.
Thus, utilize sand-blast with the situation of thickness less than the aluminium foil asperitiesization of 20 μ m under, preferably average surface roughness Ra (μ m) is defined as less than 0.20 μ m.But, when average surface roughness Ra (μ m) is too small, promptly, be under the situation of 0.026 μ m as more anodal x1, then the result from table 1 and table 2 can be clear that, can't improve positive active material and conductive agent, conductive agent and positive electrode collector, positive electrode collector and positive active material connecting airtight property separately.Based on these reasons, utilize sand-blast with the situation of thickness less than the aluminium foil asperitiesization of 20 μ m under, preferably stipulate according to the mode that makes Ra (μ m) be in the scope of 0.026 μ m＜Ra＜0.20 μ m.
Like this, because by the positive electrode collector that uses average roughness Ra (μ m) to have the relation of 0.026 μ m＜Ra＜0.20 μ m, it is big that the contact area of positive active material particle and positive electrode collector becomes, so the connecting airtight property of positive active material particle and positive electrode collector improves widely.Thus, on positive electrode collector, form the anode mixture layer, also can prevent anode mixture layer peeling off from the positive electrode collector even become big mode according to the thickness that makes the anode mixture layer.Consequently, owing to can keep the state that positive electrode collector keeps the anode mixture layer, therefore just can the LiCoO that positive active material uses will be used as in the past
2Such capacity is partly coated on the positive electrode collector of the same area.
[the 2nd embodiment]
(embodiment 1)
Except having made positive pole, made battery in the same manner with the embodiment 1 of described the 1st embodiment as followsly.
Below, the battery of so making is called battery B1 of the present invention.
At first, according to the LiFePO4 (LiFePO that makes as active material
4) reach positive active material and contain 85 a whole quality % of layer, make carbon black (the BET specific area: 70m as conductive agent
2/ g) reach a mode that positive active material contains 10 whole quality % of layer and measure after, both are mixed.Then, in this mixture, add polyacrylonitrile (PAN), make it to reach positive active material and contain 5 a whole quality % of layer, add N-methyl pyrrolidone (NMP) solution in addition in right amount as solvent as binding agent, by mixing manufacture slip.Then, this slip utilization being scraped the skill in using a kitchen knife in cookery, to coat surface roughness Ra be 0.14 μ m (Ra=0.14 μ m), maximum height R
MaxBe 1.6 μ m (R
Max=1.6 μ m), thickness be 15.0 μ m enforcement on the aluminium foil of asperities blasting treatment.
Thereafter, using electric hot tray will be coated with the electrode behind the slip after 80 ℃ of following dryings, carry out when this dried electrode is held with the plate holder of the SUS system of thickness 0.1mm, (operation between the cylinder of the PCF1075NH of Hitachi, Ltd.'s system-AM) has been carried out the 1st time calendering of described dried electrode with this to make it to pass the P.C. controller.The concrete condition of this moment is shown in following (1).
(1) the 1st time rolling condition
The slit width of cylinder: 150 μ m
The rotating speed of cylinder: 200rpm
Cylinder pass number of times; 4 times
After this, will roll after the size of electrode with 2cm * 2cm cut
Carry out 2 times holding slip coating thing with the plate holder of the SUS system of thickness 0.1mm when
The operation that makes it to pass with changing the slit width between cylinder with described identical P.C. controller is rolled described calendering electrode once more.The concrete condition of this moment is shown in following (2), (3).
(2) the 2nd times rolling condition
The slit width of cylinder: 120 μ m
The rotating speed of cylinder: 200rpm
Cylinder pass number of times: 4 times
(3) the 3rd times rolling condition
The slit width of cylinder: 100 μ m
The rotating speed of cylinder: 200rpm
Cylinder pass number of times: 4 times
At last, under 100 ℃, positive pole has been made in its vacuumize.
(embodiment 2)
Except for carbon black, use the BET specific area to be 39m as conductive agent
2Beyond the material of/g, made Experimental cell in the same manner with described embodiment 1.
Below the battery that will so make is called battery B2 of the present invention.
(embodiment 3)
Except for carbon black, use the BET specific area to be 15m as conductive agent
2Beyond the material of/g, made Experimental cell in the same manner with described embodiment 1.
Below the battery that will so make is called battery B3 of the present invention.
(embodiment 4)
Except for carbon black, use the BET specific area to be 90m as conductive agent
2Beyond the material of/g, made Experimental cell in the same manner with described embodiment 1.
Below the battery that will so make is called battery B4 of the present invention.
(embodiment 5)
Except for carbon black, use the BET specific area to be 300m as conductive agent
2Beyond the material of/g, made Experimental cell in the same manner with described embodiment 1.
Below the battery that will so make is called battery B5 of the present invention.
(embodiment 6)
Except containing 90 a whole quality % of layer, make the BET specific area of using among the described embodiment 1 be 70m according to making LiFePO4 as active material reach positive active material
2The material of/g reaches beyond a mode that positive active material contains 5 whole quality % of layer stipulates, has made Experimental cell in the same manner with described embodiment 1.
Below the battery that will so make is called battery B6 of the present invention.
(embodiment 7)
Except for carbon black, use the BET specific area of using among the described embodiment 1 is 70m as conductive agent
2The BET specific area of using among the material of/g, the described embodiment 3 is 15m
2The material of/g has been made Experimental cell according to reaching separately beyond the mixed material of mode of ratio that positive active material contains 5 whole quality % of layer in the same manner with described embodiment 1.
Below the battery that will so make is called battery B7 of the present invention.
(comparative example 1)
Except for carbon black, use the BET specific area to be 12m as conductive agent
2Beyond the material of/g, made Experimental cell in the same manner with described embodiment 1.
Below the battery that will so make is called comparison battery Y1.
(comparative example 2)
Except calendering pole plate under the rolling condition of (1) shown in the best mode that is used to carry out an invention the 1st time only, do not carry out having made Experimental cell in the same manner with described embodiment 1 beyond the 2nd time, the 3rd time the calendering.
Below the battery that will so make is called comparison battery Y2.
(experiment)
The positive active material of the described battery B1～B7 of the present invention of instrumentation and comparison battery Y1, Y2 contains the packed density of layer, then calculate the only packed density of positive active material according to this value, and under the condition identical, discharge and recharge repeatedly with the condition shown in the experiment 1 of described the 1st embodiment, investigated the discharge capacity of every 1g positive active material, its result has been illustrated in the table 3.
Can clearly confirm from table 3, use the BET specific area to be 15m
2The conductive agent that/g the is above and packed density that positive active material contains layer is made as 1.7g/cm
3Among above battery B1～B7 of the present invention, (discharging current is 0.1It～0.5It), and (discharging current is 1It～2It), can obtain very big discharge capacity when discharge at a high speed when being not only the discharge of low speed.In contrast, in little (the BET specific area: 12m of BET specific area
2/ g) compare among the battery Y1, although positive active material contains the big (packed density: 2.2g/cm of the packed density of layer
3), but when the discharge of low speed and discharge at a high speed, all can only obtain very little discharge capacity.In addition, the little (packed density: 1.6g/cm of packed density that contains layer at positive active material
3) compare among the battery Y2, because big (the BET specific area: 70m of BET specific area
2/ g), even therefore in low rates of discharge, (discharging current is that 0.1It～0.2It) also can obtain discharge capacity to a certain degree when faint discharge, yet in the discharge of low speed, when bigger discharge (discharging current is 0.5It), then discharge capacity becomes minimum, and (discharging current is 1It～2It), then can't discharge when high rate discharge.
Form that this kind result is considered to be caused by reason shown below.Promptly, in the comparison battery Y1 that has used the little conductive agent of BET specific area, diminish as the LiFePO4 of positive active material and the contact area of conductive agent, in addition, contain among the little comparison battery Y2 of packed density of layer the connecting airtight property reduction of positive active material and conductive agent and positive active material and positive electrode collector at positive active material.According to these situations, the electron conduction in the BET of conductive agent specific area or positive active material contain the packed density hour of layer, be then anodal just becomes insufficient.In contrast, using the BET specific area to be 15m
2The conductive agent that/g the is above and packed density that positive active material contains layer is made as 1.7g/cm
3Among above battery B1～B7 of the present invention, because the particle diameter of conductive agent diminishes, the conductive agent that on surface, can't disperse q.s as the LiFePO4 of positive active material, therefore the contact area of positive active material and conductive agent becomes big, and the packed density that positive active material contains layer is big, so as the LiFePO4 of positive active material and conductive agent, reach the connecting airtight property raising of positive active material and positive electrode collector.According to these situations, among battery B1～B7 of the present invention, in anodal, form the favorable conductive passage, anodal interior electron conduction improves significantly.
[the 3rd embodiment]
(embodiment 1)
As embodiment 1, used the battery B6 of the present invention shown in the embodiment 6 of described the 2nd embodiment.
(embodiment 2)
Except as positive electrode collector, use not the material of asperitiesization [surface roughness Ra is 0.026 μ m (Ra=0.026 μ m)] in addition, to make Experimental cell in the same manner with described embodiment 1.
Below the battery that will so make is called battery C of the present invention.
(experiment)
The positive active material of the described battery B6 of the present invention of instrumentation, C contains the packed density of layer, then calculate the only packed density of positive active material according to this value, and under the discharge and recharge condition identical, discharge and recharge repeatedly with the experiment 1 of described execution mode 1, investigated the discharge capacity of every 1g positive active material, its result has been illustrated in the table 4.
[table 4]
Can be clear that from described table 4, though in the discharge capacity when low speed, not there are differences between the two, in the discharge capacity when high speed, battery B6 of the present invention compares with battery C of the present invention, and it is big that discharge capacity becomes.
Forming this kind result is to be caused by reason as follows, that is: because in the battery B6 of the present invention of the aluminium foil that has used asperitiesization as positive electrode collector, have concavo-convex on the surface of positive electrode collector, therefore positive electrode collector and conductive agent, and the contact area change of positive electrode collector and positive active material greatly, can further improve the two connecting airtight property.In contrast, in used not the battery C of the present invention of the aluminium foil of asperitiesization as positive electrode collector, owing to do not exist concavo-convex on the surface of positive electrode collector, therefore positive electrode collector and conductive agent, the contact area that reaches positive electrode collector and positive active material slightly diminish, thereby make how many two connecting airtight property decreases.
(other item)
(1) among described the 1st embodiment～the 3rd embodiment, though in positive active material, only used LiFePO4, but the present invention is not limited thereto kind of a formation, needs only olivine-type lithium phosphates such as containing LiFePO4 in positive active material, just can bring into play effect of the present invention.
(2) among described the 1st embodiment～the 3rd embodiment, though sand-blast has been used in the asperities processing as positive electrode collector, but being not limited thereto, also can be wet type coating methods such as dry type coating methods such as the polishing that utilizes sand paper, the etching method that utilizes physical etch or chemical etching, vacuum vapour deposition, sputtering method, CVD method, electrolytic film plating method, electroless plating embrane method.Specifically, carry out as followsly.
Etching method
For example after being coated with resist on the positive electrode collector, the resist of not wanting part is removed, carried out etching, form concavo-convex method on the positive electrode collector surface by this resist being removed part.
The dry type coating method
Make nettedly etc. by the holder that will keep positive electrode collector, the part of positive electrode collector is covered, and the part on the surface of positive electrode collector is carried out plated film, form concavo-convex method on the positive electrode collector surface.
Wet type coating method surface
Identical with described etching method, a part of painting erosion resistant agent on positive electrode collector, or after having attached mask adhesive tape etc. on the positive electrode collector carries out plated film to the part on the surface of positive electrode collector, forms concavo-convex method on the positive electrode collector surface.
(3) among described the 1st embodiment～the 3rd embodiment,, be not limited thereto though used aluminium as positive electrode collector.But, preferred use possessed the oxidizing potential height, the also aluminium of the advantage of oxidation dissolution not of collector body when positive pole charges.
(4) among described the 2nd embodiment and the 3rd embodiment
Though carried out the calendering of 3 pole plates, be not limited to this number of times, can certainly be 1 time, 2 times, can also be more than 4 times.
(5) as nonaqueous electrolyte, be not limited to ethylene carbonate, diethyl carbonate, also can use other cyclic carbonate, linear carbonate, ester class, ring-type ethers, chain ethers, nitrile, amine etc.
As described cyclic carbonate, except described ethylene carbonate, can also enumerate propene carbonate, butylene etc., also can use the material that their part or all of hydrogen base fluoridized, can enumerate carbonic acid three fluoro propylene esters or carbonic acid fluoroethyl.
As described linear carbonate, except described diethyl carbonate, can also enumerate dimethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, ethyl propyl carbonic acid ester, carbonic acid ethyl isopropyl esters etc., also can use the material that their part or all of hydrogen fluoridized.As described ester class, can enumerate methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone etc.
As described ring-type ethers, can enumerate 1,3-dioxolanes, 4-methyl-1,3-dioxolanes, oxolane, 2-methyltetrahydrofuran, expoxy propane, 1,2-epoxy butane, 1,4-dioxane, 1,3,5-trioxane, furans, 2-methylfuran, 1,8-cineole, crown ether etc.
As described chain ethers, can enumerate 1,2-dimethoxy-ethane, diethyl ether, dipropyl ether, diisopropyl ether, butyl oxide, two hexyl ethers, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethylphenyl ether, butyl phenylate, the amyl group phenyl ether, methoxy toluene, phenylethyl ether, diphenyl ether, benzyl ether, O-dimethoxy benzene, 1,2-dimethoxy-ethane, 1,2-dibutoxy ethane, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol dibutyl ether, 1,1-dimethoxy-ethane, 1,1-diethoxyethane, triglyme, tetraethylene glycol dimethyl ether etc.
Can enumerate acetonitrile etc. as described nitrile.Can enumerate N, dinethylformamide etc. as amine.Particularly, consider, preferably use cyclic carbonates such as ethylene carbonate, propene carbonate, linear carbonate classes such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate from the viewpoint of voltage stability.
As electrolyte, be not limited to described LiPF
6, can use LiAsF
6, LiBF
4, LiCF
3SO
3, LiN (ClF
2l+1SO
2) (C
mF
2m+1SO
2) (l, m are the integer more than 1), LiC (C
pF
2p+1SO
2) (C
qF
2q+1SO
2) (C
rF
2r+1SO
2) (p, q, r are the integer more than 1) etc.In addition, also can use the difluoro shown in the Chemical formula 1 described as follows (oxalic acid) lithium borate etc.These electrolyte both can use a kind of, also can be used in combination of two or more in addition.These electrolyte preferably are dissolved in the described nonaqueous solvents according to the mode that reaches 0.1～1.5M, preferably reaches the concentration of 0.5～1.5M and use.
[changing 1]
The industrial possibility of utilizing
The present invention not only goes for mobile messages such as portable phone, PC, PDA eventually The driving power of end, and it is large-scale to go for the vehicle mounted power supply etc. of electric automobile or hybrid vehicle Battery.
Claims (12)
1. nonaqueous electrolyte battery, be the nonaqueous electrolyte battery that has possessed the positive pole that formed positive active material and contain layer on positive electrode collector, negative pole, nonaqueous electrolyte, wherein said positive active material contains in the layer, contain LiFePO4 as positive active material, it is characterized in that
Described positive electrode collector is made of the aluminium foil of thickness less than 20 μ m, and the containing the face that contact of layer with described positive active material and be carried out the asperities processing of this positive electrode collector, and through the average surface roughness Ra at the position of this processing above 0.026 μ m and below 0.14 μ m.
2. nonaqueous electrolyte battery according to claim 1 is characterized in that, described asperities processing is to adopt to utilize the grinding of sand-blast to carry out.
3. nonaqueous electrolyte battery according to claim 1 is characterized in that, the average grain diameter of described LiFePO4 is below 10 μ m.
4. nonaqueous electrolyte battery according to claim 2 is characterized in that, the average grain diameter of described LiFePO4 is below 10 μ m.
5. nonaqueous electrolyte battery according to claim 1 is characterized in that, contain at described positive active material and contain conductive agent in the layer, and the BET specific area of this conductive agent is set to 15m
2More than/the g, and described positive active material contain the layer packed density be set to 1.7g/cm
3More than.
6. nonaqueous electrolyte battery according to claim 2 is characterized in that, contain at described positive active material and contain conductive agent in the layer, and the BET specific area of this conductive agent is set to 15m
2More than/the g, and described positive active material contain the layer packed density be set to 1.7g/cm
3More than.
7. nonaqueous electrolyte battery according to claim 5 is characterized in that, the packed density that described positive active material contains layer is set to 3.15g/cm
3Below.
8. nonaqueous electrolyte battery according to claim 6 is characterized in that, the packed density that described positive active material contains layer is set to 3.15g/cm
3Below.
9. nonaqueous electrolyte battery according to claim 1 is characterized in that, applies or be attached with carbon on the surface of described positive active material particle.
10. nonaqueous electrolyte battery according to claim 2 is characterized in that, applies or be attached with carbon on the surface of described positive active material particle.
11. nonaqueous electrolyte battery according to claim 1 is characterized in that, the part at the lithium position of described positive active material is replaced by transition metal.
12. nonaqueous electrolyte battery according to claim 2 is characterized in that, the part at the lithium position of described positive active material is replaced by transition metal.
Applications Claiming Priority (3)
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|---|---|---|---|
| JP2004058375 | 2004-03-03 | ||
| JP058375/2004 | 2004-03-03 | ||
| JP080749/2004 | 2004-03-19 |
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| WO2010053200A1 (en) * | 2008-11-10 | 2010-05-14 | 株式会社エクォス・リサーチ | Positive electrode for secondary battery, secondary battery using same, collector, and battery using the collector |
| EP2437336B1 (en) * | 2009-05-27 | 2014-12-10 | LG Chem, Ltd. | Positive electrode active material, and positive electrode and lithium secondary battery comprising same |
| US9640800B2 (en) * | 2011-03-17 | 2017-05-02 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery having a positive electrode including an aluminum foil and a positive electrode active material layer formed thereon |
| CN107346831A (en) * | 2016-05-04 | 2017-11-14 | 上海奇谋能源技术开发有限公司 | A kind of method for improving lithium ion battery service life |
| CN106602030A (en) * | 2017-01-06 | 2017-04-26 | 中航锂电（洛阳）有限公司 | Low-temperature composite lithium iron phosphate material, positive plate and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346162A (en) * | 2000-09-29 | 2002-04-24 | 索尼株式会社 | Method for preparing cathode active material and non-aqueous electrolyte |
| CN1349266A (en) * | 2000-10-06 | 2002-05-15 | 索尼株式会社 | Non-aqueous electrolyte secondary cell |
| US20020106563A1 (en) * | 2000-10-06 | 2002-08-08 | Tsuyoshi Okawa | Non-aqueous electrolyte secondary cell |
| CN1382310A (en) * | 1999-10-22 | 2002-11-27 | 三洋电机株式会社 | Electrodes used in lithium batteries and rechargeable lithium batteries |
| JP2003203628A (en) * | 2001-12-28 | 2003-07-18 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery and its manufacturing method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382310A (en) * | 1999-10-22 | 2002-11-27 | 三洋电机株式会社 | Electrodes used in lithium batteries and rechargeable lithium batteries |
| CN1346162A (en) * | 2000-09-29 | 2002-04-24 | 索尼株式会社 | Method for preparing cathode active material and non-aqueous electrolyte |
| CN1349266A (en) * | 2000-10-06 | 2002-05-15 | 索尼株式会社 | Non-aqueous electrolyte secondary cell |
| US20020106563A1 (en) * | 2000-10-06 | 2002-08-08 | Tsuyoshi Okawa | Non-aqueous electrolyte secondary cell |
| JP2003203628A (en) * | 2001-12-28 | 2003-07-18 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery and its manufacturing method |
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