CN101465426A - Anode material for lithium ion battery and preparation method thereof - Google Patents
Anode material for lithium ion battery and preparation method thereof Download PDFInfo
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- CN101465426A CN101465426A CNA2007103037205A CN200710303720A CN101465426A CN 101465426 A CN101465426 A CN 101465426A CN A2007103037205 A CNA2007103037205 A CN A2007103037205A CN 200710303720 A CN200710303720 A CN 200710303720A CN 101465426 A CN101465426 A CN 101465426A
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- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 239000010405 anode material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 16
- 239000000463 material Substances 0.000 claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 15
- 229910052596 spinel Inorganic materials 0.000 claims description 12
- 239000011029 spinel Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002345 surface coating layer Substances 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims 3
- 238000005253 cladding Methods 0.000 abstract 4
- 239000004480 active ingredient Substances 0.000 abstract 2
- 229910013068 LiMxMn2-xO4 Inorganic materials 0.000 abstract 1
- 229910013064 LiMxMn2−xO4 Inorganic materials 0.000 abstract 1
- 239000002075 main ingredient Substances 0.000 abstract 1
- 229910015645 LiMn Inorganic materials 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 7
- 239000011149 active material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910018095 Ni-MH Inorganic materials 0.000 description 2
- 229910018477 Ni—MH Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- TWFMKJHWXGLVDF-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O Chemical compound [Li].[Mn](=O)(=O)(O)O TWFMKJHWXGLVDF-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an anode material for lithium ion batteries, containing LiMn2o4 active ingredient and cladding material on the surface of the LiMn2o4 active ingredient. The cladding material is a composite material rich in lithium and manganese, and the main ingredient of the cladding material is expressed into LiMxMn2-xO4 according to general expression; wherein, M can be at least one of Mg, Al, Ti, Ga, Cr, Ni and Co, and the average thickness of the surface cladding layer is 5nm-50nm. The anode material can be widely applied to the lithium secondary batteries with high charge-discharge capacity, good cycle performance and high safety, in particular to the application of the lithium ion batteries with high capacity.
Description
Technical field
The present invention relates to a kind of positive electrode that is used for lithium ion battery and preparation method thereof, specifically, relate to a kind of anode material for lithium ion battery that contains manganese/lithium composite material nanometer materials surface coated etc. and form and preparation method thereof with it.
Background technology
As everyone knows, lithium rechargeable battery is the rechargable power supplies of new generation that grows up the early 1990s in this century, its energy density height, and in light weight, volume is little, and memory-less effect does not pollute, and is a kind of green power supply.Closely during the last ten years, lithium ion battery is rapidly developed, and it occupies leading position with the higher performance advantage in mobile electronic terminal apparatus field such as notebook computer, mobile phones.
At present, along with the continual renovation of lithium rechargeable battery and perfect, its power supply that not only can be used as compact electric apparatus uses, and can expect that its power source as large-scale plant uses.Along with two hang-ups that global energy shortage and biological environment wreck are severe day by day.Electric automobile is significant to solving the energy environment problem, what can be used for electric automobile and hybrid vehicle at present mainly contains Ni-MH battery and lithium ion battery, and the specific energy of Ni-MH power cell is lower, only is 70Wh/Kg, voltage is 1.2V only, and cost is higher.And the lithium ion battery specific energy can reach 120-140Wh/Kg, can bear high current charge-discharge simultaneously, and the power density in 10 seconds can reach 1500W/kg.Therefore, lithium ion battery will become the leading role on the electrokinetic cell market gradually.Existing market grows with each passing day for the demand that thisly has high-capacitance more, has a lithium ion battery of excellent safety and output characteristic.
Lithium rechargeable battery uses material with carbon element to be negative material usually, with materials such as cobalt acid lithium, LiMn2O4s is positive electrode, and fill organic substance or polymer dielectric between positive pole and negative pole, embedding by lithium ion in anodal and negative pole or the redox reaction when taking off embedding produce electric energy.The kind of positive electrode is vital for the lithium ion battery Effect on Performance, and it has determined performance characteristics such as operating voltage, energy density and cycle life or the like of battery.
At present, the employed positive electrode active materials of business-like lithium ion battery mainly is the LiCoO with layer structure
2With LiMn with spinel structure
2O
4LiCoO wherein
2Theoretical specific capacity be about 272 MAH/grams, actual specific capacity is the positive electrode active materials that is applied to the commodity lithium ion battery the earliest in 120-140 MAH/gram scope.Because its stable performance is easy to synthesize, therefore still be widely used in the commodity lithium ion battery now.But because the natural resources shortage of Co, price is higher, therefore with LiCoO
2For the lithium ion battery of positive electrode is difficult to reduce production costs, this will become the important restraining factors of the production and the popularization of high capacity lithium ion battery.
Manganese is at the occurring in nature aboundresources, and positive spinel LiMn
2O
4Thermal stability and security performance also better.But there are many drawbacks in the use in traditional spinel lithium manganate.Such as: when battery operated during at higher temperature, owing to be in the LiMn of Charging state
2O
4In Mn
3+Can be molten to because of containing in the electrolyte that minor amount of water is acidity, cause structure damaged, thereby cause LiMn
2O
4For there are shortcomings such as serious self-discharge phenomenon and reversible capacity decay be too fast in the battery of positive electrode active materials.Circulation and shelf characteric under high temperature (more than 55 ℃) are relatively poor.
It is generally acknowledged at present that under the higher charged state or under the higher temperature a spot of transition metal ions (lithium ion) with activity leaves material body in the positive electrode, enters electrolyte, has reduced the active component in the positive electrode; And when the state of the scarce lithium of the positive electrode degree of depth, the transition metal ions tropic rearrangement in the positive electrode, material generation irreversible transition reduces the electro-chemical activity of positive electrode.In order to address this problem; people attempt to carry out surface coating processing by particle or electrode surface to existing anode material for lithium-ion batteries; change positive electrode particle surface local CHARGE DISTRIBUTION state; thereby change the surface physics and the chemical characteristic of positive electrode active materials; make positive electrode active materials can be charged to higher current potential, improve the specific capacity and the specific energy of positive electrode.For example, Chinese patent CN1416189A discloses a kind of lithium secondary battery, its positive electrode is coating modification to be carried out on the surface of active component powder handle, used clad material is semimetal, oxide or salts substances, adopt the lithium battery reversible capacity of this positive electrode preparation higher, cyclicity, fail safe have also had obvious improvement.But, also have distance with the desired safety standards of positive electrode for electrokinetic cell.
Therefore, still need to provide a kind of new positive electrode active materials, it not only has higher energy content of battery density, and charge-discharge performance is better, and its manufacturing process should be simple and direct relatively, is easy to control.Simultaneously, the product stability that helps this positive electrode active materials.The product of being produced can be used for preparing the lithium secondary battery with higher charge/discharge capacity and better cycle performance and security performance, particularly can be applicable to the positive electrode of power-type lithium ion battery of new generation, particularly the application in high capacity lithium ion battery.
Summary of the invention
The invention provides a kind of positive electrode that is used for lithium ion battery, it contains LiMn2O4 (LiMn
2O
4) active component and its surperficial clad material.Described clad material is the composite material that is rich in lithium and manganese, main component such as general formula LiM
xMn
2-xO
4Shown in, wherein M can be selected from least a among metal M g, Al, Ti, Ga, Cr, Ni and the Co, and x=0.05-0.3, the average thickness of surface coating layer are 0.5nm-500nm.
Among the present invention, its active component lithium manganate material is preferably has spinel structure.
Among the present invention, clad material LiM
xMn
2-xO
4In metallic element M be preferably selected from Mg, at least a among Al and the Ti, described x is preferably 0.05-0.15.The average thickness of coating layer is for being preferably 5nm-50nm.
A specific embodiment that is used for the positive electrode of lithium ion battery of the present invention is: described positive electrode comprises LiMn2O4 active component and the surperficial clad material thereof with spinel structure, the main component of described clad material such as general formula LiM
xMn
2-xO
4Shown in, wherein M is selected from least a among metal M g, Al and the Ti, and x=0.05-0.15, the average thickness of surface coating layer are 5nm-50nm.
The inventor thinks that the kind of clad material and character have very big influence for the performance of final positive electrode.In Chinese patent CN1416189A, as if disclosed positive electrode only be the surface that materials such as clad material such as semimetal, oxide or salt is coated on simply the active component powder, and disclosed concrete technical scheme all relates to how to coat LiCoO
2Active component, and for how handling LiMn particularly
2O
4The surface of material is not full disclosure then.And the inventor finds by repetition test, by with element M g, Al, Ti, Ga, Cr, Ni, metal substitute LiMn2O4 LiMn such as Co
2O
4In part Mn, at LiMn
2O
4The surface form a kind of new solid solution LiM
xMn
2-xO
4, can improve the active component stability of structure, thereby improve the cycle performance and the security performance of material.
Anode material for lithium-ion batteries of the present invention can adopt following method preparation:
At first, preparation active component: the lithium manganate material that manganese dioxide powder is fully mixed, obtains having after the roasting spinel structure with lithium salts or alkali, wherein in order to obtain having the lithium manganate material of spinel structure, the mol ratio of control Li and Mn is crucial.
Then, adopt the soluble-salt of M metallic element to carry out chemical reaction, thereby make metal element M substitute LiMn on the surface of active component lithium manganate material
2O
4In part Mn, the surface that the reactant that is generated is coated on active component forms colloid.And then pass through certain Technology for Heating Processing, thereby obtain can be used as the positive electrode of lithium ion battery.
Particularly, the preparation process of anode material for lithium-ion batteries of the present invention is as follows:
(1) with manganese dioxide and lithium salts or its alkali (as Li
2CO
3, LiNO
3Or LiOH.H
2O), the mol ratio in Li:Mn is (1.02～1.10): 2 ratio is fully mixed, and after 600-950 ℃ of following sintering 10-50 hour, and pulverizing obtains active component---have the lithium manganate material of spinel structure; Preferably the mol ratio of Li and Mn is (1.05～1.08): 2;
(2) step (1) gained material and water are mixed with water slurry with the ratio of 1:0.8-2.0 weight ratio; Or also can not carry out step (1) and directly the commercially available LiMn2O4 with spinel structure is mixed with water slurry in described ratio;
(3) with the aqueous solution of the soluble-salt of described M metallic element, under heating condition, the pH value〉under 7 (being preferably pH=8-13) condition, stir in the suspension of the active component that joins above-mentioned steps (2) preparation down equably, add alkaline reagent simultaneously as buffer, mixture reaction 6-12 hour; Alkaline reagent wherein can adopt NaOH or ammoniacal liquor.Usually, be reflected under the condition of heating comparatively favourablely, but should be higher than 300 ℃.
(4) through liquid, solid separation, dry, roasting, obtain anode material for lithium ion battery.
What particularly point out is anode material for lithium-ion batteries of the present invention, forms a kind of new solid solution because clad material and active component are reflected at the surface of active component, compares before the existence of this coating layer makes material and coats very big change has taken place.When its positive electrode as battery uses, because the existence of surface coating layer can make the active material of internal layer and electrolyte separate, the capacitance loss that has caused owing to the electrolyte decomposition when having lowered on the one hand because of high potential, stoped in the active material transition metal ions to electrolytical transfer on the other hand. secondly, handle the surface that occurs in active material owing to coat, therefore, the concentration that the ion of surface coating layer material causes in material far above material is carried out this kind ion doping in the concentration of material surface, the structure of stabilizing material more effectively, suppress the generation of irreversible transition, improve its cyclicity.On the contrary, because surface coating modification to the caused change of material surface character, coats the positive electrode of handling through the surface and can be charged to higher current potential and can not cause electrolytical decomposition.Because material can bear higher charging potential and seriously the lacking of the lithium ion that causes thus, through such surface coat handle positive electrode have higher specific capacity and specific energy.Therefore guaranteed when keeping material specific capacity, to have improved the cyclicity of material.
Adopt the lithium ion battery of positive electrode preparation of the present invention, have following excellent properties:
Charge/discharge capacity reaches〉105mAh/g;
Cycle performance reaches more than 500 times;
Tap density reaches 1.8g/cm;
Specific area: 1-3sqM/g.
Therefore, the positive electrode of lithium ion battery of the present invention, can be widely used in having in the lithium secondary battery of higher charge/discharge capacity and better cycle performance and security performance, the particularly application in high capacity lithium ion battery for example can be applicable to the positive electrode of power-type lithium ion battery of new generation.
Embodiment
Describe the present invention in detail below by embodiment, but the present invention is not subjected to the restriction of embodiment.
The testing standard or the method for testing of performance parameter are as follows:
Charge/discharge capacity: JJG 153-1996 standard cell vertification regulation
Cycle performance: JJG 153-1996 standard cell vertification regulation
Tap density: GB/T 5162-2006
Specific area: nitrogen adsorption method GB/T 13390-1992
Grain size analysis: laser diffractometry GB/T 19077.1-2003
Embodiment 1
Manganese dioxide (EMD) MnO is separated in power taking
2With lithium salts Li
2CO
3, be that the ratio of 1.05:2 is fully mixed in the molal quantity of Li:Mn, dehydration in 150-350 ℃ of following pre-burning 3-5 hour, passed through 700-850 ℃ of following sintering more about 20 hours, obtain spinelle manganic acid lithium material.The gained material is carried out crushing and classification handle, that is: D
10: 3 μ, D
50: 9.5 μ, D
90: 28 μ.Again with material: the ratio of water=1:1.5 is mixed with water slurry.
According to Al (NO
3)
3: LiMn
2O
4The part by weight of=1:100 is with corresponding Al (NO
3)
3Be mixed with the aqueous solution, under agitation evenly join in the above-mentioned active material suspension, dropping ammonia is as buffer simultaneously, and the pH value is controlled to be 8-9, makes mixture react the coating layer of formation (being about 15nm) about 8 hours.
Separate through solid, liquid again, from mother liquor, extract coating good solid.Dry under 200 ℃, and under 800-1000 ℃ of temperature, carry out roasting, through disperseing, obtain satisfactory anode material for lithium ion battery again.
The positive electrode of above-mentioned preparation is prepared into battery by the method for industry routine.Specifically can be referring to the described concrete steps of Chinese patent CN1416189A embodiment.
Battery product is tested: first discharge specific capacity is greater than 107mA.h/g, first charge-discharge efficiency reaches 98%, product is under rated condition, after cycle-index reaches 980 times, discharge capacity reaches 100 circulation backs of 80%, 55 ℃ of circulation capacity retention of cyclic discharge capacity for the first time〉90%.
Embodiment 2
The aqueous solution of the soluble-salt of Al is replaced by the aqueous solution of the soluble-salt of Mg, and other also can obtain satisfactory anode material for lithium ion battery with embodiment 1.
Claims (10)
1, a kind of positive electrode that is used to prepare lithium ion battery, it contains the clad material on LiMn2O4 active component and surface thereof; Described clad material is the composite material that is rich in lithium and manganese, main component such as general formula LiMxMn
2-xO
4Shown in, wherein M is selected from least a among metal M g, Al, Ti, Ga, Cr, Ni and the Co, and x=0.05-0.3, the average thickness of surface coating layer are 0.5nm one 500nm.
2, the positive electrode that is used to prepare lithium ion battery according to claim 1 is characterized in that, described M is selected from least a among Mg, Al and the Ti.
3, the positive electrode that is used to prepare lithium ion battery according to claim 1 is characterized in that, the average thickness of surface coating layer is 5nm-50nm.
4, the positive electrode that is used to prepare lithium ion battery according to claim 1 is characterized in that, described x is 0.05-0.15.
5, the positive electrode that is used to prepare lithium ion battery according to claim 1 is characterized in that, described LiMn2O4 active component has spinel structure.
6, a kind of positive electrode that is used to prepare lithium ion battery, it comprises LiMn2O4 active component and the surperficial clad material thereof with spinel structure, the main component of described clad material such as general formula LiMxMn
2-xO
4Shown in, wherein M is selected from least a among metal M g, Al and the Ti, and x=0.05-0.15, the average thickness of surface coating layer are 5nm-50nm.
7, the described preparation method who is used to prepare the positive electrode of lithium ion battery of one of a kind of claim 1-6, it may further comprise the steps:
(1) with manganese dioxide and lithium salts or its alkali, be that the ratio of 1.02～1.10:2 is fully mixed in the mol ratio of Li:Mn, after 600-950 ℃ of following sintering 10-30 hour, and pulverize and obtain active component---have the lithium manganate material of spinel structure;
(2) step (1) gained material and water are mixed with water slurry with the ratio of 1:0.8-2.0 weight ratio;
(3), under heating condition, pH value with the aqueous solution of the soluble-salt of described M metallic element〉under 7 conditions, evenly join in the suspension of active component of above-mentioned steps (2) preparation, add alkaline reagent simultaneously as buffer, mixture reaction 6-12 hour;
(4) through separation, dry, roasting, obtain anode material for lithium ion battery.
8, the preparation method of positive electrode according to claim 7 is characterized in that, the mol ratio of Li and Mn is (1.05～1.08) in the step (1): 2.
9, the preparation method of positive electrode according to claim 7 is characterized in that, pH value is controlled at 8-13 in the step (3).
10, the application of the described positive electrode of one of claim 1-6 in the preparation lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007103037205A CN101465426A (en) | 2007-12-21 | 2007-12-21 | Anode material for lithium ion battery and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007103037205A CN101465426A (en) | 2007-12-21 | 2007-12-21 | Anode material for lithium ion battery and preparation method thereof |
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ID=40805872
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102315446A (en) * | 2010-07-02 | 2012-01-11 | 株式会社半导体能源研究所 | Electrode material and method of forming electrode material |
| CN101719422B (en) * | 2010-01-08 | 2012-08-29 | 西北工业大学 | Anode material for lithium ion capacitor or battery and preparation method thereof |
| CN102969482A (en) * | 2012-12-10 | 2013-03-13 | 天津巴莫科技股份有限公司 | Method for improving stability of anode material of lithium ion battery |
| CN103035904A (en) * | 2012-12-21 | 2013-04-10 | 浙江工业大学 | Modified lithium manganate material, and preparation method and application thereof |
| CN103094554A (en) * | 2013-01-31 | 2013-05-08 | 湘潭大学 | Modified lithium manganate anode material and preparation method thereof |
| CN104321908A (en) * | 2013-02-14 | 2015-01-28 | 株式会社Lg化学 | Positive electrode active material for lithium secondary battery and lithium secondary battery containing same |
| CN104538622A (en) * | 2015-01-04 | 2015-04-22 | 合肥国轩高科动力能源股份公司 | Surface-doped rich lithium cathode material and preparation method thereof |
| CN105958027A (en) * | 2016-06-22 | 2016-09-21 | 贵州玉屏迈威科技有限公司 | Manganese-based composite positive electrode material and preparation method therefor |
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