CN1848490A - Carbonaceous lithium ion battery negative electrode material with nuclear shell structure and producing method thereof - Google Patents
Carbonaceous lithium ion battery negative electrode material with nuclear shell structure and producing method thereof Download PDFInfo
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- CN1848490A CN1848490A CNA2006100116111A CN200610011611A CN1848490A CN 1848490 A CN1848490 A CN 1848490A CN A2006100116111 A CNA2006100116111 A CN A2006100116111A CN 200610011611 A CN200610011611 A CN 200610011611A CN 1848490 A CN1848490 A CN 1848490A
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 124
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 87
- 239000010439 graphite Substances 0.000 claims abstract description 87
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 230000002687 intercalation Effects 0.000 claims abstract description 21
- 238000009830 intercalation Methods 0.000 claims abstract description 21
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000000197 pyrolysis Methods 0.000 claims abstract description 3
- 239000011859 microparticle Substances 0.000 claims description 17
- 239000003595 mist Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001720 carbohydrates Chemical class 0.000 claims description 6
- 235000014633 carbohydrates Nutrition 0.000 claims description 6
- 229910001510 metal chloride Inorganic materials 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000013081 microcrystal Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 239000001667 (E)-4-furan-2-ylbut-3-en-2-one Substances 0.000 claims description 4
- GBKGJMYPQZODMI-SNAWJCMRSA-N (e)-4-(furan-2-yl)but-3-en-2-one Chemical compound CC(=O)\C=C\C1=CC=CO1 GBKGJMYPQZODMI-SNAWJCMRSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920005546 furfural resin Polymers 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000008901 benefit Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000004224 protection Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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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Abstract
The present invention relates to a carbonaceous lithium ion cell negative electrode material with core-shell structure and its preparation method, belonging to the field of carbon material and chemical power supply technology. The described negative electrode material is formed from core portion and shell portion. The core portion is graphite obtained after the graphite intercalation compound is disintercalated, the shell portion is amorphous carbon obtained by pyrolysis of organics. Said invention also provides the concrete steps of its preparation method.
Description
Technical field
The present invention relates to carbonaceous lithium ion battery negative electrode material of a kind of nucleocapsid structure and preparation method thereof, belong to material with carbon element and technical field of chemical power.
Background technology
Lithium ion battery has been showed wide application prospect and potential great economic benefit with advantages such as high-energy-density, long circulation life, environmental protections, and in the evolution of lithium ion battery, the research and development of negative material occupies critical role always.Carbon material (comprising graphite, MCMB, organic carbon thing, petroleum coke etc.) becomes with its height ratio capacity, low electrode current potential, high cycle efficieny and long circulation life and uses and study negative material the most widely.
Graphite comprises natural micro crystal graphite, natural flake graphite, electrographite etc.Still there are some problems in undressed graphite as lithium ion battery negative material the time.On the one hand, lithium ion inserts graphite layers and can make interlamellar spacing increase in charging process, and lithium ion deviates to make graphite layers apart from reducing in the discharge process, and circulation repeatedly back graphite-structure can be because harmomegathus and destroyed repeatedly, so its cycle life is shorter; On the other hand, because the graphite surface carbon atom has a large amount of unsaturated bonds, electrolyte can decompose and formation SEI (Solid Electrolyte Interface) film at graphite surface when initial charge, makes that irreversible first amount is bigger, reduces cycle efficieny.
In order to improve cycle life and to improve cycle efficieny first, method after deliberation and its pluses and minuses are as follows:
1) utilize oxidant such as hydrogen peroxide to carry out the surface oxidation modification: the advantage method is easy, but that performance improves is limited.
2) utilizing organic substance to carry out the surface coats and high temperature cabonization: advantage is that cycle efficieny raising first is bigger, and shortcoming is that cycle life is still lower.
3) mixing lithium handles: advantage is that cycle efficieny is first increased, and shortcoming is that cycle life is not had improvement.
4) in conjunction with above method duplex surface modification: advantage is that combination property improves a lot, but cycle life still has much room for improvement.Tsing-Hua University's new carbon group has been carried out the research of this respect very early, and is used for the method for lithium ion battery negative material after finding this low cost, the little swollen graphite of high performance preparation and coating processing.
Summary of the invention
The present invention is directed to graphite cathode material because the unsaturated bond of surface carbon atom causes irreversible first amount high and discharge and recharge the harmomegathus effect that causes and destroy the problem that the negative electrode film structure makes the cycle performance difference, propose two technical schemes: with constitutionally stable amorphous carbon coated graphite surface with the irreversible first amount of reduction; Slowly take off to be inserted in the graphite granule with compound between graphite layers and form nano-micrometre level space, reserve the harmomegathus space, to improve cycle performance.
The carbonaceous lithium ion battery negative electrode material of a kind of nucleocapsid structure that the present invention proposes, granularity is 5～50 μ m, it is characterized in that: this negative material partly is made up of nuclear part and shell, the graphite that described nuclear part obtains after inserting for compound between graphite layers takes off, the amorphous carbon that described shell partly obtains for the organic substance pyrolysis.
In above-mentioned carbonaceous lithium ion battery negative electrode material, the graphite preparation method of described nuclear part is:
(1) chooses compound between graphite layers micro mist or the metal chloride MCl that raw material is the synthetic sour intercalation of chemical method or electrochemical process
xThe compound between graphite layers micro mist of intercalation, granularity are 5～50 μ m;
(2) raw material compound between graphite layers micro mist is taken off slowly slotting, describedly take off that to insert temperature be 50～350 ℃, the time is 12～72 hours, and described volumetric expansion of taking off the graphite volume ratio compound between graphite layers raw material after inserting is less than or equal to 50%.
In above-mentioned carbonaceous lithium ion battery negative electrode material, the acid of described sour intercalation comprises nitric acid, sulfuric acid, phosphoric acid, perchloric acid, various organic acids and composition thereof; Described metal chloride MCl
xM in the intercalation comprises Fe, Co, Ni, Cu, Zn, Sn, and x is 2 or 3 according to the metal valence state; The graphite that described intercalation is used is natural flake graphite, natural micro crystal graphite or electrographite.
In above-mentioned carbonaceous lithium ion battery negative electrode material, the preparation method of the shell of described amorphous carbon part is:
(1) be presoma with resin, carbohydrate, described resin is phenolic resins, furfural resin, furfural acetone resin, epoxy resin; Described carbohydrate is sugar, starch; The phosphorus content of described presoma is greater than 30%;
(2) above-mentioned presoma is dissolved in ethanol or water, makes the precursor solution of concentration 3～30wt%;
(3) graphite microparticles that will take off after inserting is dipped in the precursor solution of step 2, fully stirs, and filters redundant solution, 100～300 ℃ of dryings;
(4) with the charing under inert gas shielding of the graphite powder behind the above-mentioned impregnation drying, be warming up to 700～1100 ℃ with 30～500 ℃/h speed, be incubated 0.5～5 hour, with the stove cooling, obtain the surface and have the graphite microparticles that amorphous carbon coats.
In the shell preparation method partly of above-mentioned amorphous carbon, described step 3 is to be 20～70wt% precursor solution with concentration to be made into mass ratio be solution with taking off graphite microparticles after inserting: graphite=1: the slurry of (0.5～0.1) by spraying moulding drying, becomes the graphite powder that coats presoma.
The carbonaceous lithium ion battery negative electrode material of the nucleocapsid structure that the present invention proposes has high power capacity, the low advantage of irreversible capacity, high cycle efficieny and long circulation life first.
Description of drawings
Fig. 1 is the electrical property figure of the carbonaceous lithium ion battery negative electrode material of nucleocapsid structure of the present invention.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further:
1) with acid or metal chloride MCl
xBy chemistry or electrochemical process raw material graphite is carried out intercalation.The acid of intercalation comprises nitric acid, sulfuric acid, phosphoric acid, perchloric acid, various organic acids and composition thereof; The metal chloride MCl of intercalation
xM comprise Fe, Co, Ni, Cu, Zn, Sn, x is 2 or 3 according to the metal valence state.The graphite that intercalation is used is natural flake graphite, natural micro crystal graphite, electrographite.
2) the compound between graphite layers micro mist (granularity is 5～50 μ m) that obtains was slowly taken off slotting in 12～72 hours 50～350 ℃ of heating, obtain taking off the graphite after inserting.The volumetric expansion of taking off the graphite volume ratio compound between graphite layers raw material after inserting is smaller or equal to 50%.
3) be presoma with resin, carbohydrate, it is dissolved in ethanol or water, make the precursor solution of concentration 3～30wt%.Wherein resin is phenolic resins, furfural resin, furfural acetone resin, epoxy resin; Carbohydrate is sugar, starch.The phosphorus content of presoma is greater than 30%.
4) graphite microparticles that will take off after inserting is dipped in the precursor solution, fully stirs 0.5～6 hour, filters redundant solution, the graphite powder after 100～300 ℃ of dryings are flooded.
5) the graphite powder charing under inert gas shielding after will flooding is warming up to 700～1100 ℃ with 30～500 ℃/h speed, is incubated 0.5～5 hour, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
Perhaps adopt the precursor solution of 20～70wt% concentration and take off slotting back graphite powder and be made into mass ratio 1: (0.5～0.1) (solution: slurry graphite), by spraying moulding drying, become the graphite powder that coats presoma, then adopt identical charing method to prepare the graphite microparticles that amorphous carbon coats.
Embodiment 1
A) the common H for preparing of chemical method
2SO
4-H
2O
2It is 5～50 μ m that the system expansible graphite is crushed to particle diameter.
B) compound between graphite layers that obtains is heated 48h down at 250 ℃, slowly take off slotting.
C) the phenolic resins ethanolic solution of configuration 3wt% mass fraction, the graphite that will take off after inserting immerses in the solution, stirs 6 hours, leaves standstill filtration, the graphite powder behind 300 ℃ of dry filters 4 hours.
D) graphite powder that previous step is obtained suddenly is warming up to 1000 ℃ with 300 ℃/h speed under nitrogen protection, is incubated 4 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
The surface that the method obtains have graphite microparticles that amorphous carbon coats first cycle efficieny to change test result greater than 90%, 38 cyclic discharge capacity as follows:
Embodiment 2
A) FeCl for preparing of electrochemical process
3It is 5～50 μ m that the intercalation expansible graphite is crushed to particle diameter.
B) compound between graphite layers that obtains is heated 72h down at 350 ℃, slowly take off slotting.
C) aqueous sucrose solution of configuration 20wt% mass fraction, the graphite that will take off after inserting immerses in the solution, stirs 0.5 hour, leaves standstill filtration, the graphite powder behind 100 ℃ of dry filters 6 hours.
D) graphite powder that previous step is obtained suddenly is warming up to 700 ℃ with 500 ℃/h speed under nitrogen protection, is incubated 0.5 hour, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
Embodiment 3
A) the crystalline flake graphite micro mist of 5～50 μ m particle diameters adopts chemical method to prepare H
2SO
4The intercalated graphite intercalation compound.
B) compound between graphite layers that obtains is heated 12h down at 205 ℃, slowly take off slotting.
C) the phenolic resins ethanolic solution of configuration 5% mass fraction, the graphite that will take off after inserting immerses in the solution, stirs 2 hours, leaves standstill filtration, the graphite powder behind 200 ℃ of dry filters 6 hours.
D) graphite powder that previous step is obtained suddenly is warming up to 1000 ℃ with 250 ℃/h speed under nitrogen protection, is incubated 3 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
Embodiment 4
A) the micro crystal graphite micro mist of 5～50 μ m particle diameters uses electrochemical production FeCl
3The intercalated graphite intercalation compound.
B) compound between graphite layers that obtains is heated 50h down at 300 ℃, slowly take off slotting.
C) amidin of configuration 30wt% mass fraction, the graphite that will take off after inserting immerses in the solution, stirs 3 hours, leaves standstill filtration, the graphite powder behind 100 ℃ of dry filters 6 hours.
D) graphite powder that previous step is obtained suddenly is warming up to 900 ℃ with 200 ℃/h speed under nitrogen protection, is incubated 4 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
Embodiment 5
A) the electrographite micro mist of 5～50 μ m particle diameters uses electrochemical process to prepare CuCl
2The intercalated graphite intercalation compound.
B) compound between graphite layers that obtains is heated 50h down at 300 ℃, slowly take off slotting.
C) aqueous sucrose solution of configuration 20wt% mass fraction, the graphite that will take off after inserting immerses in the solution, stirs 60 minutes, leaves standstill filtration, the graphite powder behind 100 ℃ of dry filters 6 hours.
D) graphite powder that previous step is obtained suddenly is warming up to 1000 ℃ with 300 ℃/h speed under nitrogen protection, is incubated 4 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
Embodiment 6
A) the crystalline flake graphite micro mist of 5～50 μ m particle diameters adopts chemical method to prepare H
2SO
4The intercalated graphite intercalation compound.
B) compound between graphite layers that obtains is heated 50h down at 205 ℃, slowly take off slotting.
C) the phenolic resins ethanolic solution of configuration 70wt% concentration is inserted the back graphite powder and was made into mass ratio 1: 0.5 (solution: slurry graphite) by spraying moulding drying, becomes the graphite powder that coats presoma with taking off.
D) graphite powder that previous step is obtained suddenly is warming up to 1000 ℃ with 50 ℃/h speed under nitrogen protection, is incubated 4 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
Embodiment 7
A) the crystalline flake graphite micro mist of 5～50 μ m particle diameters adopts chemical method to prepare HNO
3The intercalated graphite intercalation compound.
B) compound between graphite layers that obtains is heated 24h down at 50 ℃, slowly take off slotting.
C) the furfural acetone resin ethanolic solution of configuration 20wt% concentration is inserted the back graphite powder and was made into mass ratio 1: 0.1 (solution: slurry graphite) by spraying moulding drying, becomes the graphite powder that coats presoma with taking off.
D) graphite powder that previous step is obtained suddenly is warming up to 1100 ℃ with 500 ℃/h speed under argon shield, is incubated 5 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
Claims (5)
1, a kind of carbonaceous lithium ion battery negative electrode material of nucleocapsid structure, granularity is 5～50 μ m, it is characterized in that: this negative material partly is made up of nuclear part and shell, the graphite that described nuclear part obtains after inserting for compound between graphite layers takes off, the amorphous carbon that described shell partly obtains for the organic substance pyrolysis.
2, carbonaceous lithium ion battery negative electrode material according to claim 1 is characterized in that, the graphite preparation method of described nuclear part is:
(1) chooses compound between graphite layers micro mist or the metal chloride MCl that raw material is the synthetic sour intercalation of chemical method or electrochemical process
xThe compound between graphite layers micro mist of intercalation, granularity are 5～50 μ m;
(2) raw material compound between graphite layers micro mist is taken off slowly slotting, describedly take off that to insert temperature be 50～350 ℃, the time is 12～72 hours, and described volumetric expansion of taking off the graphite volume ratio compound between graphite layers raw material after inserting is less than or equal to 50%.
3, carbonaceous lithium ion battery negative electrode material according to claim 2 is characterized in that, the acid of described sour intercalation comprises nitric acid, sulfuric acid, phosphoric acid, perchloric acid, various organic acids and composition thereof; Described metal chloride MCl
xM in the intercalation comprises Fe, Co, Ni, Cu, Zn, Sn, and x is 2 or 3 according to the metal valence state; The graphite that described intercalation is used is natural flake graphite, natural micro crystal graphite or electrographite.
4, carbonaceous lithium ion battery negative electrode material according to claim 1 is characterized in that, the preparation method of the shell part of described amorphous carbon is:
(1) be presoma with resin, carbohydrate, described resin is phenolic resins, furfural resin, furfural acetone resin, epoxy resin; Described carbohydrate is sugar, starch; The phosphorus content of described presoma is greater than 30%;
(2) above-mentioned presoma is dissolved in ethanol or water, makes the precursor solution of concentration 3～30wt%;
(3) graphite microparticles that will take off after inserting is dipped in the precursor solution of step 2, fully stirs, and filters redundant solution, 100～300 ℃ of dryings;
(4) with the charing under inert gas shielding of the graphite powder behind the above-mentioned impregnation drying, be warming up to 700～1100 ℃ with 30～500 ℃/h speed, be incubated 0.5～5 hour, with the stove cooling, obtain the surface and have the graphite microparticles that amorphous carbon coats.
5, carbonaceous lithium ion battery negative electrode material according to claim 4, it is characterized in that, described step 3 is that to be made into mass ratio be solution: graphite=1: the slurry of (0.5～0.1) with taking off graphite microparticles after inserting with the precursor solution of 20～70wt% concentration, by spraying moulding drying, become the graphite powder that coats presoma.
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| CN101841019A (en) * | 2010-04-30 | 2010-09-22 | 湖南大学 | Carbon cladding layer expansion graphite composite material used for lithium ion batteries and preparation method thereof |
| CN101969122A (en) * | 2010-09-14 | 2011-02-09 | 东莞市迈科新能源有限公司 | Core-shell structured carbon for cathode material of lithium ion battery and preparation method thereof |
| CN102208615A (en) * | 2011-05-05 | 2011-10-05 | 钱承亮 | Method for preparing carbon-carbon composite lithium ion battery cathode material |
| CN102420317A (en) * | 2010-09-28 | 2012-04-18 | 荣炭科技股份有限公司 | Lithium ion secondary battery cathode material and preparation method thereof |
| CN101527357B (en) * | 2009-04-24 | 2012-05-16 | 清华大学 | Nano-silicon amorphous carbon composition lithium ion battery cathode material and preparation method therefor |
| CN102496699A (en) * | 2011-12-22 | 2012-06-13 | 上海奥威科技开发有限公司 | Method for manufacturing chemical power electrode |
| CN102544458A (en) * | 2011-12-30 | 2012-07-04 | 中聚電池研究院有限公司 | Preparation method of modified graphite cathode material of lithium-ion power battery |
| CN103500665A (en) * | 2013-08-29 | 2014-01-08 | 逢甲大学 | Super capacitor with core-shell type electrodes |
| CN104085923A (en) * | 2014-07-01 | 2014-10-08 | 中国科学技术大学 | Transitional metal chalcogenide nanowire and preparation method and energy storage application thereof |
| US9054377B2 (en) | 2009-01-07 | 2015-06-09 | Tsinghua University | Cathode composition for lithium ion battery and method for fabricating the same |
| EP2650950A4 (en) * | 2011-02-15 | 2015-12-09 | Lg Chemical Ltd | Method for manufacturing anode active material |
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| JP2000123835A (en) * | 1998-10-19 | 2000-04-28 | Toyota Central Res & Dev Lab Inc | Negative electrode active material for lithium secondary battery and lithium secondary battery using the same as negative electrode active material |
| CN1339838A (en) * | 2000-08-22 | 2002-03-13 | 中国科学院化学研究所 | Carbon negative electrode material of lithium ion cell and its preparing method and use |
| CN1547278A (en) * | 2003-12-12 | 2004-11-17 | 天津大学 | Putamen type carbon cathode material for lithium ion secondary battery and preparation method thereof |
| CN100347887C (en) * | 2005-04-20 | 2007-11-07 | 深圳市贝特瑞电子材料有限公司 | Composite graphite negative electrode material for lithium ion secondary cell and its preparation method |
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