CN108023075A - A kind of hard carbon composite material of modification and preparation method thereof - Google Patents
A kind of hard carbon composite material of modification and preparation method thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000004048 modification Effects 0.000 title claims abstract description 23
- 238000002715 modification method Methods 0.000 title abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011261 inert gas Substances 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 28
- 239000012298 atmosphere Substances 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000005554 pickling Methods 0.000 claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 239000002028 Biomass Substances 0.000 claims abstract description 17
- 239000006259 organic additive Substances 0.000 claims abstract description 16
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 15
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 235000021110 pickles Nutrition 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 244000060011 Cocos nucifera Species 0.000 claims description 10
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 10
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 240000000560 Citrus x paradisi Species 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 235000012907 honey Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 229910021487 silica fume Inorganic materials 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 28
- 239000000463 material Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 238000010792 warming Methods 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 19
- 239000002245 particle Substances 0.000 description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 229910021389 graphene Inorganic materials 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000001027 hydrothermal synthesis Methods 0.000 description 13
- 238000009413 insulation Methods 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 241000894007 species Species 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- -1 metals ion Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000009656 pre-carbonization Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002539 nanocarrier Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Hard carbon composite material the present invention provides a kind of modification and preparation method thereof.Preparation method provided by the invention includes：A) pickling is carried out to organic biomass carbon source with pickle, obtains acid-leached product；B) acid-leached product is heat-treated under atmosphere of inert gases, obtains pretreatment product；C) pretreatment product, nano-catalytic carrier, organic additive and solvent are mixed, is dry, obtaining pre- carbonized product；D) the pre- carbonized product is heated to carbonization under atmosphere of inert gases, obtain carbonized product；E) carbonized product is subjected to chemical vapor deposition under hydrocarbon gas and atmosphere of inert gases, obtains modified hard carbon composite material.It according to preparation method provided by the invention, can greatly improve the chemical property of the modified hard carbon composite material of gained.
Description
Technical field
The present invention relates to battery technology field, hard carbon composite material of more particularly to a kind of modification and preparation method thereof.
Background technology
With the development of the society, the world increasingly increases the demand of the energy, and the oil reserve of the earth is extremely limited, and profit
The exhaust emissions of major product-automobile with petroleum-based energy etc. is serious, and baneful influence is caused to environment, therefore, exploitation and profit
Become the target pursued in the whole world with cleaning, the environmentally friendly energy.In recent years, lithium ion battery is due to small, matter
The features such as amount is light, higher than energy, pollution-free, and largely used by electronic products such as mobile phone, laptops, at present, lithium
Ion battery also becomes the developmental research object of pure electric automobile (EV) and hybrid electric automobile (HEV) battery, it is applied
In pure electric automobile, the conventional petroleum energy can be substituted, it is no to discharge, is pollution-free, and be applied to hybrid electric automobile, then can
Enough obvious reduction oil consumption, save petroleum-based energy and simultaneously reduce exhaust emission, and have higher economy.
Lithium ion battery mainly includes the positive electrode, the negative electrode and the separator, wherein positive and negative pole material and diaphragm material all can to lithium from
The performance of sub- battery produces large effect.Therefore, for the positive electrode of lithium ion battery, negative material and diaphragm material
Developmental research becomes the hot spot paid close attention in the industry.At present, there are many HEV dynamic lithium batteries enterprises using hard carbon as anode material
Material, such as the think of domain HEV that Honda (Honda) is released, by Blue Energy, (Honda is looked forward to the shallow HEV lithium batteries set up jointly of GS soup
Industry) dynamic lithium battery that provides, and lithium battery of daily output grace HEV etc..Hard carbon refers to be difficult to a kind of carbon material being graphitized,
It has good high rate performance, Ke Yiman as lithium cell cathode material stable structure, charge and discharge cycles service life length
The requirement of the sufficient high-power discharge and recharge of electric vehicle lithium battery.Moreover, itself and conventional electrolysis liquid (such as propene carbonate PC bases electrolyte)
Compatibility also superior to other negative materials such as graphite material etc..
But hard carbon material surface porosity is porous, moisture and oxygen in air are easily adsorbed, various C-H are formed on surface
Functional group, lithium ion easily with these functional group reactions, cause the loss of lithium ion, improve irreversible capacity, reduce first
Efficiency.
To meet the performance requirement of lithium ion battery, the prior art can generally be modified hard carbon cathode material, wherein,
Graphene is due to higher specific surface area and electrical conductivity, being commonly used for the modification of hard carbon material.Such as Publication No.
The patent application of CN104064366A obtains graphite using graphene oxide and hard carbon material by way of chemical crosslink reaction
Alkene-hard carbon composite material, however, this method preparation process is complicated, causes serious pollution to the environment, and cost of manufacture is high, it is difficult to realizes business
Industry, can not solve the realistic problem of market production application.The patent application of Publication No. CN106206047A is proposed to hard carbon
Graphene particles are directly added in material, graphene particles lamella and the non-shape of hard carbon material in the modified material that this method obtains
To arrange in pairs or groups into dominance structure, graphene sheet layer is also easily accumulated, and modified material specific surface area is deteriorated, and to lithium ion battery performance
Improvement and unobvious.Therefore, develop the negative material of excellent performance becomes one of focus of extensive concern in the industry.
The content of the invention
In view of this, it is an object of the invention to provide hard carbon composite material of a kind of modification and preparation method thereof, according to
Modified hard carbon composite material has excellent chemical property made from preparation method provided by the invention, makes lithium ion battery
Performance be obviously improved.
The present invention provides a kind of preparation method of the hard carbon composite material of modification, comprise the following steps：
A) pickling is carried out to organic biomass carbon source with pickle, obtains acid-leached product；
B) acid-leached product is heat-treated under atmosphere of inert gases, obtains pretreatment product；
C) pretreatment product, nano-catalytic carrier, organic additive and solvent are mixed, is dry, obtaining pre- carbonization
Product；
D) the pre- carbonized product is heated to carbonization under atmosphere of inert gases, obtain carbonized product；
E) carbonized product is subjected to chemical vapor deposition under hydrocarbon gas and atmosphere of inert gases, obtains modification
Hard carbon composite material.
Preferably, in the step e), the temperature of chemical vapor deposition is 1000~1800 DEG C, and the time is 1~6h, pressure
For 2~100KPa.
Preferably, in the step e), the flow of hydrocarbon gas is 30~100ml/min, and the flow of inert gas is 300
~500ml/min；
The hydrocarbon gas includes the one or more in ethane, propane, ethene, propylene and acetylene.
Preferably, in the step c), the mass ratio of pretreatment product, nano-catalytic carrier and organic additive is 9:
0.5~2: 0.5~2.
Preferably, in the step c), nano-catalytic carrier be selected from copper nanoparticle, nano-nickel powder, nano carborundum powder and
One or more in nano silica fume；
One or more of the organic additive in starch, sucrose, honey and dextrin.
Preferably, in the step d), the temperature of carbonization is 500~900 DEG C, and the time is 1~3h.
Preferably, in the step a), organic biomass carbon source is included in cocoanut shell, pomelo peel, tealeaf residue and cornstalk
One or more.
Preferably, in the step a), the acid in pickle includes one kind in hydrochloric acid, sulfuric acid, nitric acid, acetic acid and boric acid
It is or several；
The temperature of the pickling is 50~150 DEG C, and the time is 1~4h.
Preferably, the step e) includes：
E1 the carbonized product) is subjected to chemical vapor deposition under hydrocarbon gas and atmosphere of inert gases, is deposited
Product；
E2) by the sedimentation products, cooling is handled under hydrogen and atmosphere of inert gases, obtains modified hard carbon composite wood
Material.
Present invention also offers a kind of hard carbon composite material of modification, as the preparation method system described in above-mentioned technical proposal
.
The present invention provides a kind of preparation method of the hard carbon composite material of modification, including：A) with pickle to organic life
Material carbon source carries out pickling, obtains acid-leached product；B) acid-leached product is heat-treated under atmosphere of inert gases, obtains pretreatment production
Thing；C) pretreatment product, nano-catalytic carrier, organic additive and solvent are mixed, is dry, obtaining pre- carbonized product；
D) the pre- carbonized product is heated to carbonization under atmosphere of inert gases, obtain carbonized product；E) by the carbonized product in hydrocarbon
Chemical vapor deposition is carried out under class gas and atmosphere of inert gases, obtains modified hard carbon composite material.There is provided according to the present invention
Preparation method made from modified hard carbon composite material include hard carbon material, nano-catalytic carrier and graphene, wherein, receive
Rice catalytic carrier is coated on hard carbon surface as physics filling covering material or is filled in hard carbon loose and porous structure, reduces hard
The side reaction of carbon surface and moisture in air and oxygen, reduces the loss of lithium ion in lithium-ion battery electrolytes；Meanwhile nanometer
Catalytic carrier surface deposited the graphene layer with two-dimentional regular hexagon structure, it is with the splendid embedding lithium of lithium ion/de- lithium
Ability, can significantly improve the chemical property of material, its chemical property is much better than the carbon-coating knot of conventional vapor deposition method generation
Structure；Moreover, nano-carrier, as the bridge formation between graphene and hard carbon, three forms dominance structure collocation, make what gained was modified
The chemical property of hard carbon composite material greatly improves.Present invention also offers hard carbon modified made from the preparation method is compound
Material.Test result indicates that the present invention obtained by modification hard carbon composite material specific surface area >=1395m2/ g, electric discharge are held
Amount >=600mAh/g, 50 weeks circulation volume conservation rate >=95% of first charge-discharge efficiency >=78%, the.
Embodiment
The present invention provides a kind of preparation method of the hard carbon composite material of modification, comprise the following steps：
A) pickling is carried out to organic biomass carbon source with pickle, obtains acid-leached product；
B) acid-leached product is heat-treated under atmosphere of inert gases, obtains pretreatment product；
C) pretreatment product, nano-catalytic carrier, organic additive and solvent are mixed, is dry, obtaining pre- carbonization
Product；
D) the pre- carbonized product is heated to carbonization under atmosphere of inert gases, obtain carbonized product；
E) carbonized product is subjected to chemical vapor deposition under hydrocarbon gas and atmosphere of inert gases, obtains modification
Hard carbon composite material.
According to the present invention, pickling is carried out to organic biomass carbon source with pickle first, obtains acid-leached product.
Wherein, the species of the organic biomass carbon source is not particularly limited, and is well known to those skilled in the art organic
Biomass carbon source, preferably includes the one or more in cocoanut shell, pomelo peel, tealeaf residue and cornstalk.In the present invention, institute
State the acid in pickle and preferably include one or more in hydrochloric acid, sulfuric acid, nitric acid, acetic acid and boric acid.The matter of the pickle
It is preferably 1%~30% to measure fraction.In the present invention, the mass ratio of the pickle and organic biomass carbon source is preferably (3~5)
∶1；In certain embodiments, the mass concentration of pickle is close to 1g/cm3, pickle can be measured with volume, that is, control pickling
The volume of liquid and the mass ratio of organic biomass carbon source are (1200~2000) mL: 400g.The present invention is using pickle to organic
Biomass carbon source carries out pickling, on the one hand can be good at disperseing organic biomass carbon source, on the other hand can preferably remove
Part metals ion such as calcium ion, magnesium ion and potassium ion etc. in organic biomass carbon source, are acted on by above-mentioned both sides
Help to improve the treatment effect of organic biomass carbon source in subsequent processing and lifting properties of product.In the present invention, the acid
The temperature washed is preferably 50~150 DEG C；The time of the pickling is preferably 1~4h.
In the present invention, after pickling, preferably further include and washed and dried；The temperature of the washing is preferably 50~
150℃；The time of the washing is preferably 1~4h；It is furthermore preferred that the temperature and time and the temperature and time phase of pickling of washing
Together；It is dried after washing, obtains acid-leached product.
According to the present invention, after acid-leached product is obtained, acid-leached product is heat-treated under atmosphere of inert gases, obtains pre- place
Manage product.
Wherein, the species of the inert gas is not particularly limited, and is species well known to those skilled in the art, bag
Include the one or more in nitrogen, helium, neon, argon gas, Krypton and xenon.The temperature of the heat treatment is preferably 200~500
℃；The time of the heat treatment is preferably 1~4h.The heating rate of the heat treatment is preferably 5~50 DEG C/min.The present invention is logical
Overheating Treatment removes the material for being difficult to be carbonized in the organic biomass carbon source after pickling, including part carbohydrate, cellulose etc., makes
Be converted into the material that can be discharged such as tarry impurities etc., these materials can be discharged with inert gas, be conducive to improve follow-up
Be carbonized effect.
In the present invention, after the heat treatment, preferably further include and crushed and Screening Treatment；The mode of the crushing does not have
Have specifically limited, pass through ball mill grinding in certain embodiments；Screening Treatment is carried out after crushing, in certain embodiments, is used
Large particulate matter is removed in 600 mesh sieve mesh screen blankings, obtains pretreatment product；The particle diameter of screening gained pretreatment product is preferably 10~
20μm.Through above-mentioned heat treatment and crush and the uniform mixing for after Screening Treatment, being conducive to additive solubility, scattered and carbonization
Deng.
According to the present invention, after obtaining pretreatment product, by the pretreatment product, nano-catalytic carrier, organic additive
With solvent mixing, drying, pre- carbonized product is obtained.
Wherein, the nano-catalytic carrier is preferably in copper nanoparticle, nano-nickel powder, nano carborundum powder and nano silica fume
One or more；More preferably copper nanoparticle and/or nano-nickel powder.The particle diameter of the nano-catalytic carrier is preferably 0.5~
5nm.In the present invention, the nano-catalytic carrier can produce the progress that catalytic action is catalyzed follow-up graphene deposition reaction, together
When the carrier as carrying graphene again, graphene is deposited on its surface, be to realize one of key that hard carbon is modified.
In the present invention, the organic additive is preferably the one or more in starch, sucrose, honey and dextrin.This hair
Bright addition organic additive, it is excessive that it potentially acts as above-mentioned nano-catalytic carrier and pretreatment product both physical characteristic differences
Material between pontic, ensure that the two is dispersed in subsequent processes, therefore, pretreatment product, nano-catalytic carrier
And organic additive acts synergistically, the hard carbon composite material of the modification of excellent performance could be obtained.In the present invention, the pretreatment
The mass ratio of product, nano-catalytic carrier and organic additive is preferably 9: 0.5~2: 0.5~2.
In the present invention, the species of the solvent is not particularly limited, and can be dissolved each addO-on therapy and be disperseed, preferably
Including the one or more in water, ethanol, isopropanol, acetone, isobutanol and DMC (i.e. dimethyl carbonate).In the present invention, solvent
Additive amount be not particularly limited, can ensure that whole system is uniformly mixed, preferably make mixed system viscosity be in 100
~2000CP, the solid content of whole system is 10%~50%.
The present invention does not have special limit to the hybrid mode of pretreatment product, nano-catalytic carrier, organic additive and solvent
All materials, can be uniformly mixed by system.The temperature of the mixing is preferably 25~100 DEG C.After mixing, to its into
Row drying, the present invention are not particularly limited the mode of the drying, in order to avoid each material layering of drying process, drying process
The dispersion effect and raising drying efficiency of middle reinforcement material, it is preferred to use spray drying.After drying, pre- carbonized product is obtained.
According to the present invention, after pre- carbonized product is obtained, the pre- carbonized product is heated into carbon under atmosphere of inert gases
Change, obtain carbonized product.
Wherein, the inert gas is consistent with the inert gas described in above-mentioned technical proposal, repeats no more.The carbonization
Temperature be preferably 500~900 DEG C；The time of the carbonization is preferably 1~3h.After carbonization, each component is mainly by pyrocarbon
Turn to hard carbon component, organic biomass carbon source and organic additive are carbonized as hard carbon, are mainly included in gained carbonized product
Hard carbon and nano-catalytic carrier, nano-catalytic carrier physics filling bag cover hard carbon, are coated on hard carbon surface or are filled in hard carbon and dredge
In loose loose structure, optimization structure is formed, reduces hard carbon surface and the side reaction of moisture in air and oxygen, reduces lithium-ion electric
The loss of lithium ion in the electrolyte of pond, is conducive to improve product chemical property.
In the present invention, after the carbonization, cooling and crushing and screening are preferably further included.After carbonization, preferably first cool down
To room temperature, crushed afterwards, the mode of the crushing is not particularly limited, in certain embodiments using ball mill grinding；Powder
Sieved after broken, sieved in certain embodiments using 600 mesh sieve nets, the particle diameter of screening gained carbonized product is preferably
10~20 μm.
According to the present invention, after carbonized product is obtained, by the carbonized product under hydrocarbon gas and atmosphere of inert gases
Chemical vapor deposition is carried out, obtains modified hard carbon composite material.
In the present invention, the inert gas is consistent with the inert gas described in above-mentioned technical proposal, repeats no more；Using
Atmosphere of inert gases can avoid introducing oxygen generation explosion and combustion reaction occurs for hard carbon；The flow of the inert gas is preferred
For 300~500ml/min.In the present invention, the species of the hydrocarbon gas is not particularly limited, for known to those skilled in the art
Hydrocarbon gas, preferably include the one or more in ethane, propane, ethene, propylene and acetylene.It is described in the present invention
The flow of hydrocarbon gas is preferably 30~100ml/min.In the present invention, the temperature of the chemical vapor deposition is preferably 1000~
1800℃；The time of chemical vapor deposition is preferably 1~6h；The pressure of chemical vapor deposition is preferably 2~100KPa；Chemical gas
Mutually the heating rate in the temperature-rise period of deposition is preferably 5~50 DEG C/min.In chemical vapour deposition reaction, hydrocarbon gas is being received
Rice catalyst support surface deposited graphite alkene simultaneously produces hydrogen, and nano-carrier is as the bridge formation between graphene and hard carbon, three
Dominance structure collocation is formed, greatly improves the chemical property of the modified hard carbon composite material of gained.
In the present invention, after carrying out chemical vapor deposition and obtaining sedimentation products, preferably further include sedimentation products in hydrogen
Handled with cooling under atmosphere of inert gases.Wherein, inert gas is consistent with the inert gas described in above-mentioned technical proposal, no longer
Repeat；Inert gas can guarantee system be in oxygen-free environment, lift cooling-down effect and take away back vapour deposition after remain
Remaining hydrocarbon gas；In the present invention, the flow of inert gas is preferably 1000~2000mL/min.Meanwhile introducing hydrogen can
Further avoid remaining hydrocarbon gas that side reaction occurs in temperature-fall period and generates non-graphite alkenes carbide, influence inertia
The protecting effect of gas；In the present invention, the flow of hydrogen is preferably 250~750mL/min.The cooling is preferably dropped to room temperature,
Rate of temperature fall is preferably 5~50 DEG C/s.After cooling, modified hard carbon composite material is obtained.
The present invention provides a kind of preparation method of the hard carbon composite material of modification, according to preparation method provided by the invention
The hard carbon composite material of obtained modification includes hard carbon material, nano-catalytic carrier and graphene, wherein, nano-catalytic carrier
Hard carbon surface is coated on as physics filling covering material or is filled in hard carbon loose and porous structure, reduces hard carbon surface and sky
The side reaction of moisture and oxygen in gas, reduces the loss of lithium ion in lithium-ion battery electrolytes；Meanwhile nano-catalytic carrier table
Face deposited the graphene layer with two-dimentional regular hexagon structure, it, can be significantly with the splendid embedding lithium of lithium ion/de- lithium ability
The chemical property of material is improved, its chemical property is much better than the carbon-coating structure of conventional vapor deposition method generation；Moreover, nanometer
For carrier as the bridge formation between graphene and hard carbon, three forms dominance structure collocation, makes the modified hard carbon composite material of gained
Chemical property greatly improve.
Present invention also offers a kind of hard carbon composite material of modification, as the preparation method system described in above-mentioned technical proposal
.The hard carbon composite material of the modification has excellent chemical property, test result indicates that, the modification obtained by the present invention
Hard carbon composite material specific surface area >=1395m2/ g, discharge capacity >=600mAh/g, first charge-discharge efficiency >=78%, the
50 weeks circulation volume conservation rate >=95%.
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Embodiment 1
400g coconut shell powders are added in the sulfuric acid solution that 1200mL mass fractions are 20%, in 90 in hydrothermal reaction kettle
Take out and filter after DEG C pickling 2h, then wash 2h and drying, obtain acid-leached product.Gained acid-leached product is placed in tube furnace
In, insulation heat treatment 2h, is then cooled to room temperature after being warming up to 300 DEG C under nitrogen atmosphere with 10 DEG C/min；With cooled product：
Zirconia ball：Deionized water=1:10:1 mass ratio ball milling 4h at 500 rpm, wherein, Φ 10 in zirconia ball：The matter of Φ 2
Amount is than being 3:2；Ball milling is finished after dry 14h at 70 DEG C, with 600 mesh sieve mesh screens point, obtains the pre- place that particle diameter is 10~20 μm
Manage product.With pretreatment product：Copper nanoparticle：Sucrose=9:1:Three is mixed and is placed in hydrothermal reaction kettle by 1 mass ratio,
300mL deionized waters are added after dispersed 1h at 150 DEG C, is then spray-dried at 120 DEG C, obtains pre- carbonized product.
The pre- carbonized product of gained is placed in tube furnace, insulation heat treatment 2h after being warming up to 700 DEG C under nitrogen atmosphere with 10 DEG C/min,
Then room temperature is down to, with 600 mesh sieve mesh screens point, obtains the carbonized product that particle diameter is 10~20 μm.Gained carbonized product is placed in
In tube furnace, after being warming up to 1200 DEG C with 10 DEG C/min, methane gas is passed through with 50mL/min, 500mL/min is passed through nitrogen, and
Control the pressure of tube furnace to be vapor-deposited for 50KPa, room temperature is down to 10 DEG C/s after 3h, is continued in temperature-fall period to tubular type
Nitrogen is passed through with 2000mL/min in stove, 500mL/min is passed through hydrogen, after cooling, obtains modified hard carbon composite material.
Embodiment 2
400g coconut shell powders are added in the sulfuric acid solution that 1200mL mass fractions are 30%, in 90 in hydrothermal reaction kettle
Take out and filter after DEG C pickling 4h, then wash 4h and drying, obtain acid-leached product.Gained acid-leached product is placed in tube furnace
In, insulation heat treatment 2h, is then cooled to room temperature after being warming up to 500 DEG C under nitrogen atmosphere with 20 DEG C/min；With cooled product：
Zirconia ball：Deionized water=1:10:1 mass ratio ball milling 4h at 500 rpm, wherein, Φ 10 in zirconia ball：The matter of Φ 2
Amount is than being 3:2；Ball milling is finished after dry 14h at 70 DEG C, with 600 mesh sieve mesh screens point, obtains the pre- place that particle diameter is 10~20 μm
Manage product.With pretreatment product：Copper nanoparticle：Sucrose=9:2:Three is mixed and is placed in hydrothermal reaction kettle by 2 mass ratio,
300mL deionized waters are added after dispersed 1h at 150 DEG C, is then spray-dried at 120 DEG C, obtains pre- carbonized product.
The pre- carbonized product of gained is placed in tube furnace, insulation heat treatment 3h after being warming up to 700 DEG C under nitrogen atmosphere with 20 DEG C/min,
Then room temperature is down to, with 600 mesh sieve mesh screens point, obtains the carbonized product that particle diameter is 10~20 μm.Gained carbonized product is placed in
In tube furnace, after being warming up to 1200 DEG C with 20 DEG C/min, methane gas is passed through with 50mL/min, 500mL/min is passed through nitrogen, and
Control the pressure of tube furnace to be vapor-deposited for 39.9KPa, room temperature is down to 15 DEG C/s after 3h, is continued in temperature-fall period to pipe
Nitrogen is passed through with 2000mL/min in formula stove, 500mL/min is passed through hydrogen, after cooling, obtains modified hard carbon composite material.
Embodiment 3
400g coconut shell powders are added in the sulfuric acid solution that 1200mL mass fractions are 10%, in 90 in hydrothermal reaction kettle
Take out and filter after DEG C pickling 1h, then wash 1h and drying, obtain acid-leached product.Gained acid-leached product is placed in tube furnace
In, insulation heat treatment 2h, is then cooled to room temperature after being warming up to 200 DEG C under nitrogen atmosphere with 10 DEG C/min；With cooled product：
Zirconia ball：Deionized water=1:10:1 mass ratio ball milling 4h at 500 rpm, wherein, Φ 10 in zirconia ball：The matter of Φ 2
Amount is than being 3:2；Ball milling is finished after dry 14h at 70 DEG C, with 600 mesh sieve mesh screens point, obtains the pre- place that particle diameter is 10~20 μm
Manage product.With pretreatment product：Copper nanoparticle：Sucrose=9:0.5:Three is mixed and is placed in hydro-thermal reaction by 0.5 mass ratio
In kettle, 300mL deionized waters are added after dispersed 1h at 150 DEG C, is then spray-dried at 120 DEG C, obtains pre- carbonization
Product.The pre- carbonized product of gained is placed in tube furnace, after being warming up to 700 DEG C under nitrogen atmosphere with 5 DEG C/min at heat preservation hot
1h is managed, is then down to room temperature, with 600 mesh sieve mesh screens point, obtains the carbonized product that particle diameter is 10~20 μm.By gained carbonized product
It is placed in tube furnace, after being warming up to 1200 DEG C with 50 DEG C/min, methane gas is passed through with 50mL/min, 500mL/min is passed through nitrogen
Gas, and control the pressure of tube furnace to be vapor-deposited for 30KPa, room temperature is down to after 3h with 5 DEG C/s, continue in temperature-fall period to
Nitrogen is passed through with 2000mL/min in tube furnace, 500mL/min is passed through hydrogen, after cooling, obtains modified hard carbon composite material.
Embodiment 4
400g coconut shell powders are added in the sulfuric acid solution that 1200mL mass fractions are 20%, in 90 in hydrothermal reaction kettle
Take out and filter after DEG C pickling 2h, then wash 2h and drying, obtain acid-leached product.Gained acid-leached product is placed in tube furnace
In, insulation heat treatment 2h, is then cooled to room temperature after being warming up to 300 DEG C under nitrogen atmosphere with 10 DEG C/min；With cooled product：
Zirconia ball：Deionized water=1:10:1 mass ratio ball milling 4h at 500 rpm, wherein, Φ 10 in zirconia ball：The matter of Φ 2
Amount is than being 3:2；Ball milling is finished after dry 14h at 70 DEG C, with 600 mesh sieve mesh screens point, obtains the pre- place that particle diameter is 10~20 μm
Manage product.With pretreatment product：Nano-nickel powder：Sucrose=9:1:Three is mixed and is placed in hydrothermal reaction kettle by 1 mass ratio,
300mL deionized waters are added after dispersed 1h at 150 DEG C, is then spray-dried at 120 DEG C, obtains pre- carbonized product.
The pre- carbonized product of gained is placed in tube furnace, insulation heat treatment 2h after being warming up to 700 DEG C under nitrogen atmosphere with 10 DEG C/min,
Then room temperature is down to, with 600 mesh sieve mesh screens point, obtains the carbonized product that particle diameter is 10~20 μm.Gained carbonized product is placed in
In tube furnace, after being warming up to 1200 DEG C with 10 DEG C/min, methane gas is passed through with 50mL/min, 500mL/min is passed through nitrogen, and
Control the pressure of tube furnace to be vapor-deposited for 30KPa, room temperature is down to 10 DEG C/s after 3h, is continued in temperature-fall period to tubular type
Nitrogen is passed through with 2000mL/min in stove, 500mL/min is passed through hydrogen, after cooling, obtains modified hard carbon composite material.
Comparative example 1
400g coconut shell powders are added in the sulfuric acid solution that 1200mL mass fractions are 10%, in 90 in hydrothermal reaction kettle
Take out and filter after DEG C pickling 2h, then wash 2h and drying, obtain acid-leached product.Gained acid-leached product is placed in tube furnace
In, insulation heat treatment 2h, is then cooled to room temperature after being warming up to 300 DEG C under nitrogen atmosphere with 10 DEG C/min；With cooled product：
Zirconia ball：Deionized water=1:10:1 mass ratio ball milling 4h at 500 rpm, wherein, Φ 10 in zirconia ball：The matter of Φ 2
Amount is than being 3:2；Ball milling is finished after dry 14h at 70 DEG C, with 600 mesh sieve mesh screens point, obtains the pre- place that particle diameter is 10~20 μm
Manage product.With pretreatment product：Sucrose=9:Three is mixed and is placed in hydrothermal reaction kettle by 1 mass ratio, is added 300mL and is gone
Then ionized water is spray-dried at 120 DEG C after dispersed 1h at 150 DEG C, obtains pre- carbonized product.Gained is carbonized in advance
Product is placed in tube furnace, and insulation heat treatment 2h, is then down to room after being warming up to 700 DEG C under nitrogen atmosphere with 10 DEG C/min
Temperature, with 600 mesh sieve mesh screens point, obtains the carbonized product that particle diameter is 10~20 μm.Gained carbonized product is placed in tube furnace, with
After 10 DEG C/min is warming up to 1200 DEG C, methane gas is passed through with 50mL/min, 500mL/min is passed through nitrogen, and controls tube furnace
Pressure be vapor-deposited for 30KPa, room temperature is down to 10 DEG C/s after 3h, continue in temperature-fall period into tube furnace with
2000mL/min is passed through nitrogen, and 500mL/min is passed through hydrogen, after cooling, obtains hard carbon material.
Comparative example 2
400g coconut shell powders are placed in tube furnace, heat preservation hot after being warming up to 300 DEG C under nitrogen atmosphere with 10 DEG C/min
2h is handled, is then cooled to room temperature；With cooled product：Zirconia ball：Deionized water=1:10:1 mass ratio is at 500 rpm
Ball milling 4h, wherein, Φ 10 in zirconia ball：The mass ratio of Φ 2 is 3:2；Ball milling is finished after dry 14h at 70 DEG C, with 600 mesh
Sieve sieves, and obtains the pretreatment product that particle diameter is 10~20 μm.With pretreatment product：Copper nanoparticle：Sucrose=9:1:1 matter
Amount is placed in hydrothermal reaction kettle than three is mixed, and adds 300mL deionized waters after dispersed 1h at 150 DEG C, then
It is spray-dried at 120 DEG C, obtains pre- carbonized product.The pre- carbonized product of gained is placed in tube furnace, under nitrogen atmosphere with
Insulation heat treatment 2h, is then down to room temperature after 10 DEG C/min is warming up to 700 DEG C, with 600 mesh sieve mesh screens point, obtain particle diameter for 10~
20 μm of carbonized product.Gained carbonized product is placed in tube furnace, after being warming up to 1200 DEG C with 10 DEG C/min, with 50mL/min
Methane gas is passed through, 500mL/min is passed through nitrogen, and controls the pressure of tube furnace to be vapor-deposited for 30KPa, with 10 after 3h
DEG C/s is down to room temperature, continues to be passed through nitrogen into tube furnace with 2000mL/min in temperature-fall period, 500mL/min is passed through hydrogen,
After cooling, hard carbon material is obtained.
Comparative example 3
400g coconut shell powders are added in the sulfuric acid solution that 1200mL mass fractions are 30%, in 90 in hydrothermal reaction kettle
Take out and filter after DEG C pickling 2h, then wash 2h and drying, obtain acid-leached product.Gained acid-leached product is placed in tube furnace
In, insulation heat treatment 2h, is then cooled to room temperature after being warming up to 300 DEG C under nitrogen atmosphere with 10 DEG C/min；With cooled product：
Zirconia ball：Deionized water=1:10:1 mass ratio ball milling 4h at 500 rpm, wherein, Φ 10 in zirconia ball：The matter of Φ 2
Amount is than being 3:2；Ball milling is finished after dry 14h at 70 DEG C, with 600 mesh sieve mesh screens point, obtains the pre- place that particle diameter is 10~20 μm
Manage product.With pretreatment product：Copper nanoparticle：Sucrose=9:1:Three is mixed and is placed in hydrothermal reaction kettle by 1 mass ratio,
300mL deionized waters are added after dispersed 1h at 150 DEG C, is then spray-dried at 120 DEG C, obtains pre- carbonized product.
The pre- carbonized product of gained is placed in tube furnace, insulation heat treatment 2h after being warming up to 700 DEG C under nitrogen atmosphere with 10 DEG C/min,
Then room temperature is down to, with 600 mesh sieve mesh screens point, obtains the carbonized product that particle diameter is 10~20 μm.Gained carbonized product is placed in
In tube furnace, it is warming up to 1200 DEG C with 10 DEG C/min and keeps the temperature carbonization 4h, obtain hard carbon material.
Embodiment 5
Specific surface area test is carried out to material made from embodiment 1~4 and comparative example 1~3, as a result referring to table 1.
Button half-cell is assembled into using material made from embodiment 1~4 and comparative example 1~3, is specially：By made from
Specimen material, binding agent (PVDF) and acetylene black press 90:10:5 mass ratio is sufficiently mixed uniformly in 1-methyl-2-pyrrolidinone,
Gained slurry is applied on copper foil, negative plate is made through 110 DEG C of vacuum dryings, rolling.Using metal lithium sheet as to electrode,
Celgard 2400 is membrane, the LiP6+EC of 1mol/L：DEC:DMC (volume ratios 1：1：1) it is electrolyte, is assembled into simulation button
Formula half-cell.Electrochemical property test, charge-discharge velocity 0.1C, voltage range are carried out on Land CT2100 discharge and recharge instrument
For 0.001~1.0V.Electrochemical property test the results are shown in Table 1.
The performance test results of material obtained by 1 embodiment of the present invention of table and comparative example
From above test result, according to hard carbon composite material energy modified made from preparation method provided by the invention
Enough significantly improve chemical property.
Specific case used herein is set forth the principle of the present invention and embodiment, and above example is said
It is bright to be only intended to help the method and its core concept for understanding the present invention, including best mode, and also so that this area is appointed
What technical staff can put into practice the present invention, including manufacture and using any device or system, and implement the method for any combination.
It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, can also be right
The present invention carries out some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.This hair
The scope of bright patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other implementation
Example.If these other embodiments, which have, is similar to the structural element of claim character express, or if they include with
Equivalent structural elements of the character express of claim without essence difference, then these other embodiments should also be included in right will
In the range of asking.
Claims (10)
1. the preparation method of the hard carbon composite material of a kind of modification, it is characterised in that comprise the following steps：
A) pickling is carried out to organic biomass carbon source with pickle, obtains acid-leached product；
B) acid-leached product is heat-treated under atmosphere of inert gases, obtains pretreatment product；
C) pretreatment product, nano-catalytic carrier, organic additive and solvent are mixed, is dry, obtaining pre- carbonized product；
D) the pre- carbonized product is heated to carbonization under atmosphere of inert gases, obtain carbonized product；
E) carbonized product is subjected to chemical vapor deposition under hydrocarbon gas and atmosphere of inert gases, obtains modified hard carbon
Composite material.
2. preparation method according to claim 1, it is characterised in that in the step e), the temperature of chemical vapor deposition
For 1000~1800 DEG C, the time is 1~6h, and pressure is 2~100KPa.
3. preparation method according to claim 1 or 2, it is characterised in that in the step e), the flow of hydrocarbon gas is
30~100ml/min, the flow of inert gas is 300~500ml/min；
The hydrocarbon gas includes the one or more in ethane, propane, ethene, propylene and acetylene.
4. preparation method according to claim 1, it is characterised in that in the step c), pretreatment product, nano-catalytic
The mass ratio of carrier and organic additive is 9: 0.5~2: 0.5~2.
5. the preparation method according to claim 1 or 4, it is characterised in that in the step c), nano-catalytic carrier is selected from
One or more in copper nanoparticle, nano-nickel powder, nano carborundum powder and nano silica fume；
One or more of the organic additive in starch, sucrose, honey and dextrin.
6. preparation method according to claim 1, it is characterised in that in the step d), the temperature of carbonization for 500~
900 DEG C, the time is 1~3h.
7. preparation method according to claim 1, it is characterised in that in the step a), organic biomass carbon source includes
One or more in cocoanut shell, pomelo peel, tealeaf residue and cornstalk.
8. preparation method according to claim 1, it is characterised in that in the step a), the acid in pickle includes salt
One or more in acid, sulfuric acid, nitric acid, acetic acid and boric acid；
The temperature of the pickling is 50~150 DEG C, and the time is 1~4h.
9. preparation method according to claim 1, it is characterised in that the step e) includes：
E1 the carbonized product) is subjected to chemical vapor deposition under hydrocarbon gas and atmosphere of inert gases, obtains sedimentation products；
E2) by the sedimentation products, cooling is handled under hydrogen and atmosphere of inert gases, obtains modified hard carbon composite material.
10. the hard carbon composite material of a kind of modification, it is characterised in that by preparation method according to any one of claims 1 to 9
It is made.
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| CN110085813A (en) * | 2019-01-16 | 2019-08-02 | 上海普澜特夫精细化工有限公司 | A kind of hard carbon composite material and preparation method |
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| CN113764645A (en) * | 2021-09-15 | 2021-12-07 | 河北坤天新能源科技有限公司 | Preparation method of hard carbon composite material with three-dimensional structure |
| CN114156456A (en) * | 2021-12-08 | 2022-03-08 | 西北工业大学 | High-capacity fast charge-discharge graphene@hard carbon composites and their preparation methods and applications in sodium-ion batteries |
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| CN117457932A (en) * | 2023-10-26 | 2024-01-26 | 张家港德泰储能装备有限公司 | Weldable conductive bipolar plate for acid, alkaline and neutral flow batteries and preparation method thereof |
| CN117720093A (en) * | 2023-12-29 | 2024-03-19 | 温州大学碳中和技术创新研究院 | Preparation method of low-polarization sodium ion battery hard carbon anode material |
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