CN102208635A - Lithium ion battery cathode material and manufacturing method thereof and lithium ion battery - Google Patents
Lithium ion battery cathode material and manufacturing method thereof and lithium ion battery Download PDFInfo
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- CN102208635A CN102208635A CN2011101197032A CN201110119703A CN102208635A CN 102208635 A CN102208635 A CN 102208635A CN 2011101197032 A CN2011101197032 A CN 2011101197032A CN 201110119703 A CN201110119703 A CN 201110119703A CN 102208635 A CN102208635 A CN 102208635A
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- centrophyten
- corrosive liquid
- lithium ion
- ion battery
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 96
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 239000010406 cathode material Substances 0.000 title abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 214
- 239000000377 silicon dioxide Substances 0.000 claims description 107
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 105
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 94
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 85
- 229910052799 carbon Inorganic materials 0.000 claims description 84
- 239000000463 material Substances 0.000 claims description 80
- 235000013312 flour Nutrition 0.000 claims description 71
- 239000007788 liquid Substances 0.000 claims description 65
- 229910052710 silicon Inorganic materials 0.000 claims description 63
- 239000010703 silicon Substances 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 56
- 239000002131 composite material Substances 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000007833 carbon precursor Substances 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 47
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 46
- 239000011863 silicon-based powder Substances 0.000 claims description 42
- 239000011247 coating layer Substances 0.000 claims description 35
- 239000000725 suspension Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 150000007529 inorganic bases Chemical class 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 230000007797 corrosion Effects 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000000935 solvent evaporation Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 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 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 210000000481 breast Anatomy 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 239000011295 pitch Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 238000005255 carburizing Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 21
- 239000000843 powder Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 238000001132 ultrasonic dispersion Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 11
- 239000011263 electroactive material Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002153 silicon-carbon composite material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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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
Abstract
The invention provides a lithium ion battery cathode material and a manufacturing method thereof and a lithium ion battery. The lithium ion battery cathode material comprises central particles and shells for coating the central particles, wherein the outside diameter of the central particles is smaller than the inside diameter of the shells. Because the outside diameter of the central particles is smaller than the inside diameter of the shells and the central particles are limited in the shells in the lithium ion battery cathode material, pulverization fall of the central particles can be relieved and even eliminated, the capacity attenuation of the lithium ion battery can be relieved, and the cycle performance of the lithium ion battery is improved.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of lithium ion battery negative material and preparation method thereof, and lithium ion battery.
Background technology
Lithium ion battery is as a kind of rechargeable battery, and it relies on lithium ion to embed between positive pole and negative pole or takes off embedding and come work.Therefore lithium ion battery is used widely at portable electric appts owing to can reuse.
At present, lithium ion battery is negative pole with the graphitized carbon, the compound that contains lithium is for anodal, the layer structure space that this graphitized carbon negative material is had provides the place for the storage of lithium, but its theoretical specific capacity is about 372mAh/g, therefore, the storage lithium ability of graphitized carbon is lower, is difficult to satisfy fields such as electric automobile to the big capacity of lithium ion battery, high-power requirement.
The researcher finds that the theoretical specific capacity of silicon and tin is higher, and especially silicon reaches 4200mAh/g.Yet, the lithium ion battery of making as negative material of silica-base material is accompanied by serious bulk effect (expansion of volume and contraction) in the process of doff lithium, this causes electroactive material (mainly the referring to silicon) powder of detached on the electrode easily, cause the capacity attenuation of lithium ion battery, and then cause the lithium ion battery cycle performance to reduce.
For this reason, Chinese patent CN03116070.0 has proposed a kind of used as negative electrode of Li-ion battery silicon-aluminum/carbon composite, this negative material is dispersible carrier with carbon, silicon-aluminum is scattered in the carbon carrier, utilize silicon, the aluminium embedding lithium effect under different potentials, can make the volumetric expansion of negative pole occur in different current potentials, thereby alleviate the bulk effect of negative pole, and then reduce the powder of detached of electroactive material on the electrode.
Chinese patent CN02112180.X discloses a kind of Si-C composite material of used as negative electrode of Li-ion battery height ratio capacity, it is a dispersible carrier with carbon class material, siliceous class material is dispersed in the carrier, wherein, siliceous class material is silicon, Si oxide, silicon alloy or siliceous compound, being about to silicon class material (active material) is distributed in other activity or the non-active material (as carbon class material), thereby form the Si-C-X negative material, in the formula, X is oxygen, the alloy in the silicon alloy or other element in the silicon compound in the Si oxide.Reduce the powder of detached of electroactive material on the electrode by the little characteristics of Si-C-X negative material bulk effect.
Though above-mentioned two kinds of lithium ion battery negative materials can reduce the bulk effect of electrode to a certain extent, thereby can alleviate the powder of detached of electroactive material on the electrode.Yet in above-mentioned two kinds of negative materials, carbon and silicon are that the compound or carbon of simple physics coats silicon closely, and the bulk effect when this discharges and recharges alleviation is very limited, and when the negative material volumetric expansion, the electroactive material powder of detached is still very serious.Therefore, general silicon-based anode material is through after tens circulations, and capacity is difficult to maintain more than the 200mAh/g.
Summary of the invention
At the above-mentioned problems in the prior art, the present invention proposes a kind of lithium ion battery negative material, it can reduce the bulk effect of charge and discharge process effectively, thereby alleviates even elimination electroactive material powder of detached phenomenon, and then can improve the cycle performance of lithium ion battery.
The present invention also proposes a kind of manufacture method of lithium ion battery negative material, can reduce the bulk effect of charge and discharge process effectively by the lithium ion battery negative material of this method acquisition, thereby alleviate even elimination electroactive material powder of detached phenomenon, and then improve the cycle performance of lithium ion battery negative material.
The present invention also proposes a kind of lithium ion battery, and it is the specific capacity height not only, and electroactive material is difficult for powder of detached, stable cycle performance, long service life.
In order to achieve the above object, the present invention proposes a kind of lithium ion battery negative material, the housing that comprises centrophyten and coat described centrophyten, and the external diameter of described centrophyten is less than the internal diameter of described housing.
Preferably, described centrophyten is silicon powder particle or coated with silica silicon powder particle.
Preferably, the particle diameter of described centrophyten is 0.05～5 μ m.
Preferably, described housing is the carbon coating layer of porous.
The present invention also provides a kind of manufacture method of lithium ion battery negative material, may further comprise the steps:
Step s10 obtains centrophyten;
Step s20 makes coating layer on the surface of described centrophyten, thereby forms composite material;
Step s30 reduces the outside dimension of described centrophyten, thereby forms the housing of internal diameter greater than described centrophyten external diameter in the periphery of described centrophyten.
Preferably, described coating layer is a carbon coating layer.
Preferably, described carbon coating layer obtains by following steps:
Carbon precursor polymer and solvent are mixed with carbon precursor polymer solution;
Described centrophyten is added described carbon precursor polymer solution and forms carbon precursor polymer suspension-turbid liquid;
Make the solvent evaporation in the described carbon precursor polymer suspension-turbid liquid, thereby obtain the centrophyten of carbon precursor polymer overmold;
Make the carbonization of described carbon precursor polymer, obtain described carbon coating layer, thereby form composite material with surface at described centrophyten;
Perhaps, carbon precursor polymer is mixed with described centrophyten ball milling, so that the described centrophyten of carbon precursor polymer overmold;
Make the carbonization of described carbon precursor polymer, obtain described carbon coating layer, thereby form composite material with surface at described centrophyten.
Preferably, described carbon precursor polymer is a kind of or wherein several mixture in polyvinyl alcohol, butadiene-styrene rubber breast, sodium carboxymethylcellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, phenolic resins, pitch, epoxy resin, glucose, sucrose, cellulose, the starch.
Preferably, the carbonization in inert atmosphere of described carbon precursor polymer, carburizing temperature is 400～1200, carbonization time is 0.1～12 hour.
Preferably, described inert atmosphere is the mist of nitrogen, argon gas or argon gas and hydrogen.
Preferably, described centrophyten is a silica flour, reduces the outside dimension of described centrophyten with forms of corrosion by corrosive liquid.
Preferably, described corrosive liquid is hydrofluoric acid and the formulated corrosive liquid of hydrogen peroxide, and in described corrosive liquid, the mass concentration of described hydrofluoric acid is 3%～20%, and the mass concentration of described hydrogen peroxide is 1%～15%; Perhaps,
Described corrosive liquid is the corrosive liquid that hydrofluoric acid and nitric acid system form, and in described corrosive liquid, the mass concentration of described hydrofluoric acid is 3%～40%, and the mass concentration of described nitric acid is 5%～35%; Perhaps,
Described corrosive liquid is an inorganic base, and the mass concentration of described inorganic base is 0.4%～30%.
Preferably, described centrophyten is the coated with silica silicon powder particle, reduces the outside dimension of described centrophyten with forms of corrosion by corrosive liquid.
Preferably, described corrosive liquid is hydrofluoric acid and the formulated corrosive liquid of hydrogen peroxide, and the mass concentration of described hydrofluoric acid is 3%～20%, and the mass concentration of described hydrogen peroxide is 1%～15%; Perhaps,
Described corrosive liquid is the corrosive liquid that hydrofluoric acid and nitric acid system form, and the mass concentration of described hydrofluoric acid is 3%～40%, and the mass concentration of described nitric acid is 5%～35%; Perhaps,
Described corrosive liquid is an inorganic base, and the mass concentration of described inorganic base is 0.4%～30%; Perhaps,
Described corrosive liquid is a hydrofluoric acid solution, and its mass concentration is 3%～40%.
Preferably, described corrosive liquid is hydrofluoric acid and the formulated corrosive liquid of hydrogen peroxide, and the mass concentration of described hydrofluoric acid is 3%～15%, and the mass concentration of described hydrogen peroxide is 3%～10%.
Preferably, described corrosive liquid is the corrosive liquid that hydrofluoric acid and nitric acid system form, and the mass concentration of described hydrofluoric acid is 3%～15%, and the mass concentration of described nitric acid is 5%～15%.
Preferably, described inorganic base is NaOH or potassium hydroxide or sodium carbonate.
Preferably, the mass ratio of described composite material and described corrosive liquid is 1: 10～1: 1000, and etching time is 0.5～100 hour.
Preferably, the mass ratio of described composite material and described corrosive liquid is 1: 10～1: 50, and etching time is 2～10 hours.
Preferably, the mass ratio of described carbon precursor polymer and described centrophyten is 1: 20～2: 1.
Preferably, described coated with silica silicon powder particle obtains in the following manner:
Silica flour is scattered in the ethanolic solution to obtain silica flour suspension;
Tetraethoxysilane is mixed the acquisition mixed liquor with ethanol;
Described mixed liquor is added in the described silica flour suspension;
Add catalyst and make described tetraethoxysilane generation hydrolysis, thereby obtain the coated with silica silicon powder particle.
Preferably, tetraethoxysilane is mixed with ethanol in the step that obtains mixed liquor, the volume ratio of described tetraethoxysilane and ethanol is 1: 1～1: 2.
Preferably, described mixed liquor is being added in the step of described silica flour suspension, the addition of described mixed liquor added according to the mol ratio of silicon in silicon in the tetraethoxysilane and the described silica flour suspension in 3: 1～1: 1.
Preferably, described catalyst is the acid of 0.1～2mo l/L or the alkali of 0.05～1mo l/L.
The present invention also provides a kind of lithium ion battery, comprises negative pole, and described negative pole adopts described lithium ion battery negative material provided by the invention to make.
Compared with prior art, the present invention has following beneficial effect:
The lithium ion battery negative material that the present invention proposes since the external diameter of centrophyten less than the internal diameter of housing, promptly be provided with the cushion space that expands for centrophyten in enclosure interior, and, housing is limited in centrophyten in the housing, thereby can alleviate even eliminate the centrophyten powder of detached, thereby alleviate the capacity attenuation of lithium ion battery, improve its cycle performance.
The manufacture method of lithium ion battery negative material provided by the invention is simple, and flow process is short, only need three steps can obtain lithium ion battery negative material, so this manufacture method is easy to industrialization.And, the lithium ion battery negative material that obtains by the manufacture method of lithium ion battery negative material provided by the invention since the external diameter of centrophyten less than the internal diameter of housing, the cushion space that promptly provides centrophyten to expand in the inside of housing, and housing is limited in centrophyten in the housing, thereby can alleviate even eliminate the defective of the housing powder of detached that the volumetric expansion because of centrophyten causes, and then can alleviate the capacity attenuation of lithium ion battery, improve its cycle performance.
Lithium ion battery provided by the invention is because lithium ion battery negative material can be alleviated the volumetric expansion of charge and discharge process effectively, thus alleviation even elimination electroactive material powder of detached phenomenon.Therefore, lithium ion battery provided by the invention has excellent cycle performance.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, to do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below, apparently, accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the structure diagram of the lithium ion battery negative material of the present invention's proposition;
Fig. 2 is the flow chart of the manufacture method of the lithium ion battery negative material of the present invention's proposition;
Fig. 3 is the flow chart of the manufacture method of coated with silica silicon powder particle;
The cycle performance collection of illustrative plates of lithium ion battery under constant current 0.1C that Fig. 4 obtains for the lithium ion battery negative material manufacture method that adopts the embodiment of the invention one to propose;
The cycle performance collection of illustrative plates of lithium ion battery under constant current 0.1C that Fig. 5 obtains for the lithium ion battery negative material manufacture method that adopts the embodiment of the invention five to propose; And
Fig. 6 is the XRD figure spectrum of lithium ion battery negative material provided by the invention.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, lithium ion battery negative material that the present invention is proposed below in conjunction with accompanying drawing and preparation method thereof, lithium ion battery are described in detail.
Fig. 1 sees also Fig. 1 for the structure diagram of the lithium ion battery negative material of the present invention's proposition.Lithium ion battery negative material comprises centrophyten 1 and housing 2, centrophyten 1 is coated by housing 2, and the external diameter of centrophyten 1 is less than the internal diameter of housing 2, this not only can provide the expansion space for the expansion of centrophyten 1, and housing 2 is limited in centrophyten 1 in the housing 2, thereby can alleviate even eliminate centrophyten 1 powder of detached, thereby alleviate the capacity attenuation of lithium ion battery, improve its cycle performance.
In the present embodiment, centrophyten 1 is silicon powder particle or coated with silica silicon powder particle, and the outside dimension of centrophyten 1 is 0.05～5 μ m.Housing 2 is the carbon coating layer of loose structure, and the space in the carbon coating layer of loose structure can be used for further holding the volumetric expansion in the silicon embedding lithium process, thereby slows down even eliminate the phenomenon of electroactive material powder of detached.
The lithium ion battery negative material that present embodiment provides since the external diameter of centrophyten 1 less than the internal diameter of housing 2, promptly be provided with the cushion space that expands for centrophyten 1 in housing 2 inside, and, housing 2 is limited in centrophyten 1 in the housing 2, thereby can alleviate even eliminate centrophyten 1 powder of detached, thereby alleviate the capacity attenuation of lithium ion battery, improve its cycle performance.
Fig. 2 is the flow chart of the manufacture method of a kind of lithium ion battery negative material of the present invention's proposition.See also Fig. 2, the manufacture method of lithium ion battery negative material may further comprise the steps:
Step s10 obtains centrophyten.
The present embodiment centrophyten is a silica flour, and the particle diameter of silica flour is 0.05～5 μ m.
Step s20 makes coating layer on the surface of centrophyten, thereby forms composite material.
Coating layer is a carbon coating layer, that is, make carbon coating layer in the periphery of silica flour, thereby form carbon-silicon composite material.The manufacture method of carbon coating layer may further comprise the steps:
Step s21 is mixed with carbon precursor polymer solution with carbon precursor polymer and solvent.
At step s21, carbon precursor polymer is a kind of or wherein several mixture in polyvinyl alcohol, butadiene-styrene rubber breast, sodium carboxymethylcellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, phenolic resins, pitch, epoxy resin, glucose, sucrose, cellulose, the starch.Solvent is selected according to carbon precursor polymer, as long as can be with carbon precursor polymer dissolution, this and prior art be identical.
Step s22 adds described carbon precursor polymer solution with described centrophyten and forms suspension-turbid liquid.
Take by weighing a certain amount of silica flour, it is added in carbon precursor polymer solution, ultrasonic dispersion 5～100 minutes forms carbon precursor polymer suspension-turbid liquid so that silica flour is dispersed in the carbon precursor polymer solution fully.The mass ratio of described carbon precursor polymer and described silica flour is 1: 20～2: 1, preferred 1: 10～3: 2.
Step s23 makes the solvent evaporation in the described carbon precursor polymer suspension-turbid liquid, thereby obtains the centrophyten of carbon precursor polymer overmold.
Stirring and heating contain the carbon precursor polymer suspension-turbid liquid of silica flour, make the solvent evaporation in it, thereby obtain carbon precursor polymer overmold silicon powder particle, promptly form carbon-silicon composite material.Heating-up temperature is decided according to solvent types, as long as can be with solvent evaporation, this be same as the prior art.
Need to prove that carbon precursor polymer overmold silicon powder particle also can obtain by direct hybrid mode, is specially:
Take by weighing carbon precursor polymer and silica flour respectively, the mass ratio of described carbon precursor polymer and described silica flour is 1: 20～2: 1, preferred 1: 10～3: 2; Obtain carbon precursor polymer overmold silicon powder particle by the ball milling hybrid mode then.Ball milling mixes and can adopt mode same as the prior art to carry out, and as 400 rev/mins of the rotating speeds of ball mill, the ball milling time is 1～3 hour.
Step s24 makes the carbonization of described carbon precursor polymer, obtains described carbon coating layer with the surface at described silica flour, thereby forms composite material.
Make the carbonization of carbon precursor polymer under inert atmosphere, the temperature of carbonization is 400～1200 ℃, preferred 700～1000 ℃; The time of carbonization is 0.1～12 hour, preferred 1～5 hour.Inert atmosphere can be made of the mist of nitrogen, argon gas or argon gas and hydrogen.
The carbon coating layer that is obtained by step s24 is the coating layer of porous, and carbon coating layer coats silica flour, i.e. carbon-silicon composite material, or title carbon coating silicon composite closely.
Need to prove that after the carbonization of carbon precursor polymer, carbon coats silicon composite and tends to caking, at this moment, can be ground into granule by lapping mode, to help follow-up corrosion treatment.
Step s30 reduces the outside dimension of described centrophyten, thereby forms the housing of internal diameter greater than described centrophyten in the periphery of described centrophyten.
Present embodiment is to utilize corrosive liquid to reduce the outside dimension of described centrophyten with forms of corrosion, thereby obtains the composite negative pole material that hollow carbon sphere coats silicon.
The composite material that carbon is coated silicon adds in the corrosive liquid, and carbon coats the composite material of silicon and the mass ratio of corrosive liquid is 1: 10～1: 1000, preferred 1: 10～1: 50; Etching time is 0.5～100 hour, preferred 2～10 hours; The temperature of corrosive liquid is a room temperature.In corrosion process, corrosive liquid will reduce as the outside dimension of the silicon powder particle of centrophyten.After the corrosion, clean the composite material that carbon coats silicon,, thereby obtain ion cathode material lithium then in oven dry below 100 ℃ with distilled water.By corrosion, make carbon coating layer form loose structure, and make the internal diameter size of the outside dimension of silicon powder particle less than carbon coating layer.
In the present embodiment, corrosive liquid is hydrofluoric acid and the formulated corrosive liquid of hydrogen peroxide.In described corrosive liquid, the mass concentration of described hydrofluoric acid is 3%～20%, preferred 5%～15%; The mass concentration of described hydrogen peroxide is 1%～15%, preferred 3%～10%.
Perhaps, corrosive liquid is the corrosive liquid that hydrofluoric acid and nitric acid system form.In corrosive liquid, the mass concentration of described hydrofluoric acid is 3%～40%, preferred 5%～15%; The mass concentration of described nitric acid is 5%～35%, preferred 5%～15%.
Perhaps, described corrosive liquid is an inorganic base, and the mass concentration of described inorganic base is 0.4%～30%, preferred 4%～20%.Inorganic base can be sodium hydroxide solution or potassium hydroxide solution or sodium carbonate liquor or other alkaline solution.
Need to prove that the manufacture method of above-mentioned lithium ion battery negative material is to be centrophyten with the silica flour, but the present invention is not limited thereto, centrophyten also can adopt the coated with silica silicon powder particle.Fig. 3 is the flow chart of the manufacture method of coated with silica silicon powder particle.See also Fig. 3, the manufacture method of coated with silica silicon powder particle is as follows:
To take by weighing particle diameter be the silica flour of 0.05～5 μ m and put into ethanolic solution, and with ultrasonic dispersion 15～30 minutes, silica flour is dispersed in the ethanolic solution, forms silica flour suspension.The volumetric concentration of ethanolic solution is 50%～80%, and the concentration of silica flour is 0.5～3mol/L in silica flour suspension.
Step s200 mixes the acquisition mixed liquor with tetraethoxysilane with ethanol.
The volume ratio of described tetraethoxysilane and ethanol is 1: 1～1: 2.
Need to prove that the order of step s100 and step s200 can be exchanged, also can carry out simultaneously, to reduce the process time.
Step s300 adds described mixed liquor in the described silica flour suspension.
Mixed liquor mixes according to the mole of silicon with silica flour suspension, is specially, and the mol ratio of silicon is 3: 1～1: 1 in silicon in the tetraethoxysilane and the described silica flour suspension.
Step s400 adds catalyst, so that described tetraethoxysilane generation hydrolysis, thereby obtain the coated with silica silicon powder particle.
Add catalyst and make described tetraethoxysilane generation hydrolysis and generate silicon dioxide, the reaction time is 1～3 hour, and the coated with silica of generation is at silicon powder surface, thus acquisition coated with silica silica flour.Catalyst can be acid, example hydrochloric acid, acetic acid etc., and the concentration of acid is 0.1～2mol/L; Also can be alkali, as NaOH, potassium hydroxide etc., the concentration of alkali be 0.05～1mol/L.
The mixed liquor that step s200 is obtained slowly adds in the silica flour suspension of step s100 acquisition, and
Need to prove that step s400 also can merge with step s300, promptly adds catalyst when mixed liquor is added silica flour suspension simultaneously.Perhaps, catalyst also can directly add in the silica flour suspension of step s100 acquisition, like this, mixed liquor is being added step s 300 in the process of silica flour suspension, tetraethoxysilane generation hydrolysis reacts immediately, and this can simplify production procedure, makes production technology more easy to operate.
Step s500 filters, cleans, dries.
The coated with silica silicon powder particle is leached, and clean with distilled water, oven dry then, thus obtain the coated with silica silicon powder particle.
Need to prove, if with the coated with silica silicon powder particle as centrophyten, the making step of lithium ion battery negative material and the technological parameter of employing are basic identical, difference only is, corrosive liquid or inorganic base that corrosive liquid, hydrofluoric acid and the nitric acid system that corrosive liquid not only can select the hydrofluoric acid mentioned among the step s30 and hydrogen peroxide to be configured to forms, can also select mass concentration for use is 3%～40% hydrofluoric acid.
Embodiment one
A. obtain centrophyten, as centrophyten, the particle diameter of silica flour is 0.05 μ m to present embodiment with silica flour.
B. make carbon coating layer at silicon powder surface and form the composite material that carbon coats silicon.
Weigh 0.2 gram phenolic resins and be dissolved in the 30mL ethanol, add 4 gram silica flours, ultrasonic dispersion 100min; Get the compound of thickness after stirring evaporation then, the drying; It is changed in the porcelain boat, be warmed up to 1200 ℃ under nitrogen protection, and be incubated 0.1 hour, take out the cooling back, obtains the composite material that carbon coats silicon.
C. the composite material that carbon is coated silicon joins the mixed liquor of 100mL hydrofluoric acid and hydrogen peroxide, and wherein the hydrofluoric acid mass fraction is 3%, and the mass fraction of hydrogen peroxide is 1%, and continuous stirring 100h; Then the gained suspended matter is filtered, and fully wash, dry, thereby obtain the negative material that carbon coats silicon, promptly obtain the composite negative pole material that hollow carbon sphere coats silicon with distilled water.
Embodiment two
A. obtain centrophyten, as centrophyten, the particle diameter of silica flour is 0.5 μ m to present embodiment with silica flour.
B. make carbon coating layer at silicon powder surface and form the composite material that carbon coats silicon.
Weigh 0.2 gram SBR emulsion and be dissolved in the 30mL ethanol, add 2 gram silica flours, ultrasonic dispersion 80min; Get the compound of thickness after stirring evaporation then, the drying; It is changed in the porcelain boat, be warmed up to 1000 ℃ under nitrogen protection, and be incubated 5 hours, take out the cooling back, obtains the composite material that carbon coats silicon.
C. the composite material that carbon is coated silicon joins the mixed liquor of 50mL hydrofluoric acid and hydrogen peroxide, and wherein the hydrofluoric acid mass fraction is 5%, and the mass fraction of hydrogen peroxide is 3%, and continuous stirring 10h; Then the gained suspended matter is filtered, and fully wash, dry, thereby obtain the negative material that carbon coats silicon, promptly obtain the composite negative pole material that hollow carbon sphere coats silicon with distilled water.
Embodiment three
A. obtain centrophyten, as centrophyten, the particle diameter of silica flour is 1 μ m to present embodiment with silica flour.
B. make carbon coating layer at silicon powder surface and form the composite material that carbon coats silicon.
Weigh 0.3 gram methacrylic acid and be dissolved in the 40mL ethanol, add 0.2 gram silica flour, ultrasonic dispersion 20min; Get the compound of thickness after stirring evaporation then, the drying; It is changed in the porcelain boat, be warmed up to 700 ℃ under nitrogen protection, and be incubated 1 hour, take out the cooling back, obtains the composite material that carbon coats silicon.
C. the composite material that carbon is coated silicon joins the mixed liquor of 100mL hydrofluoric acid and hydrogen peroxide, and wherein the hydrofluoric acid mass fraction is 15%, and the mass fraction of hydrogen peroxide is 10%, and continuous stirring 5h; Then the gained suspended matter is filtered, and fully wash, dry, thereby obtain the negative material that carbon coats silicon, promptly obtain the composite negative pole material that hollow carbon sphere coats silicon with distilled water.
Embodiment four
A. obtain centrophyten, as centrophyten, the particle diameter of silica flour is 5 μ m to present embodiment with silica flour.
B. make carbon coating layer at silicon powder surface and form the composite material that carbon coats silicon.
Weigh 0.2 gram phenolic resins and be dissolved in the 30mL ethanol, add 0.1 gram silica flour, ultrasonic dispersion 5min; Get the compound of thickness after stirring evaporation then, the drying; It is changed in the porcelain boat, be warmed up to 400 ℃ under nitrogen protection, and be incubated 12 hours, take out the cooling back, obtains the composite material that carbon coats silicon.
C. the composite material that carbon is coated silicon joins the mixed liquor of 100mL hydrofluoric acid and hydrogen peroxide, and wherein the hydrofluoric acid mass fraction is 20%, and the mass fraction of hydrogen peroxide is 15%, and continuous stirring 0.5h; Then the gained suspended matter is filtered, and fully wash, dry, thereby obtain the negative material that carbon coats silicon, promptly obtain the composite negative pole material that hollow carbon sphere coats silicon with distilled water.
Embodiment five
A. obtain centrophyten, the present embodiment centrophyten is the particle of coated with silica silica flour.
The particle of coated with silica silica flour obtains by following steps: weigh 1.4 gram silica flours and be mixed in 30mL ethanol and the 30mL distilled water, ultrasonic dispersion 30min obtains silica flour suspension, adds the hydrochloric acid that 6mL concentration is 0.1mol/L then.The tetraethoxysilane of getting 42mL concentration simultaneously and be 1g/mL mixes with 42mL ethanol and obtains mixed liquor, mixed solution is slowly joined in the silica flour suspension, and continue to stir 2h; After reaction is finished, with the gained suspension filtered, and with distilled water washing, oven dry, thereby obtain the coated with silica silicon powder particle.
B. make carbon coating layer at silicon powder surface and form the composite material that carbon coats silicon.
Weigh 0.2 gram polyvinyl alcohol and be dissolved in 30mL ethanol and the 30mL distilled water, add 0.6 gram coated with silica silicon powder particle, ultrasonic dispersion 20min; Get the compound of thickness after stirring evaporation then, the drying; It is changed in the porcelain boat, be warmed up to 800 ℃ under nitrogen protection, and be incubated 4 hours, take out the cooling back, obtains the composite material that carbon coats silicon.
C. the composite material that carbon is coated silicon joins the mixed liquor of 100mL hydrofluoric acid and nitric acid, and wherein the hydrofluoric acid mass fraction is 3%, and the mass fraction of nitric acid is 5%, and continuous stirring 2h; Then the gained suspended matter is filtered, and fully wash, dry, thereby obtain the negative material that carbon coats silicon, promptly obtain the composite negative pole material that hollow carbon sphere coats silicon with distilled water.
Embodiment six
A. obtain centrophyten, the present embodiment centrophyten is the particle of coated with silica silica flour.
The particle of coated with silica silica flour obtains by following steps: the silica flour that weighs 1.4 grams is dissolved in 45mL ethanol and 15mL distilled water, and ultrasonic dispersion 15min obtains silica flour suspension, adds the ammoniacal liquor that 60mL concentration is 1mol/L then.The tetraethoxysilane of getting 10.4mL concentration simultaneously and be lg/mL mixes with 20.8mL ethanol and obtains mixed liquor, mixed solution is slowly joined in the silica flour suspension, and continue to stir 3h; After reaction is finished, with the gained suspension filtered, and with distilled water washing, oven dry, thereby obtain the coated with silica silicon powder particle.
B. make carbon coating layer at silicon powder surface and form the composite material that carbon coats silicon.
Weigh 0.2 gram polyvinyl alcohol and be dissolved in 30mL ethanol and the 30mL distilled water, add 3.8 gram coated with silica silicon powder particles, ultrasonic dispersion 20min; Get the compound of thickness after stirring evaporation then, the drying; It is changed in the porcelain boat, be warmed up to 900 ℃ under nitrogen protection, and be incubated 3 hours, take out the cooling back, obtains the composite material that carbon coats silicon.
C. the composite material that carbon is coated silicon joins the mixed liquor of 100mL hydrofluoric acid and nitric acid, and wherein the hydrofluoric acid mass fraction is 5%, and the mass fraction of nitric acid is 15%, and continuous stirring 40h; Then the gained suspended matter is filtered, and fully wash, dry, thereby obtain the negative material that carbon coats silicon, promptly obtain the composite negative pole material that hollow carbon sphere coats silicon with distilled water.
Embodiment seven
A. obtain centrophyten, the present embodiment centrophyten is the particle of coated with silica silica flour.
The particle of coated with silica silica flour obtains by following steps: weigh 1.4 gram silica flours and be dissolved in 30mL ethanol and 10mL distilled water, ultrasonic dispersion 30min obtains silica flour suspension, adds the NaOH that 3mL concentration is 0.05mol/L then.The tetraethoxysilane of getting 24.96mL concentration simultaneously and be 1g/mL mixes with 37.44mL ethanol and obtains mixed liquor, mixed solution is slowly joined in the silica flour suspension, and continue to stir 4h; After reaction is finished, with the gained suspension filtered, and with distilled water washing, oven dry, thereby obtain the coated with silica silicon powder particle.
B. make carbon coating layer at silicon powder surface and form the composite material that carbon coats silicon.
Weigh 0.2 gram polyvinyl alcohol and be dissolved in 30mL ethanol and the 30mL distilled water, add 2 gram coated with silica silicon powder particles, ultrasonic dispersion 20min; Get the compound of thickness after stirring evaporation then, the drying; It is changed in the porcelain boat, be warmed up to 850 ℃ under nitrogen protection, and be incubated 8 hours, take out the cooling back, obtains the composite material that carbon coats silicon.
C. the composite material that carbon is coated silicon joins the mixed liquor of 100mL hydrofluoric acid and nitric acid, and wherein the hydrofluoric acid mass fraction is 15%, and the mass fraction of nitric acid is 35%, and continuous stirring 30h; Then the gained suspended matter is filtered, and fully wash, dry, thereby obtain the negative material that carbon coats silicon, promptly obtain the composite negative pole material that hollow carbon sphere coats silicon with distilled water.
Embodiment eight
A. obtain centrophyten, the present embodiment centrophyten is the particle of coated with silica silica flour.
The particle of coated with silica silica flour obtains by following steps: the silica flour that weighs 1.4 grams is dissolved in 30mL ethanol and 30mL distilled water, and ultrasonic dispersion 30min obtains silica flour suspension, adds the hydrochloric acid that 30mL concentration is 2mol/L then.The tetraethoxysilane of getting 166.4mL concentration simultaneously and be 1g/mL mixes with 200mL ethanol and obtains mixed liquor, mixed solution is slowly joined in the silica flour suspension, and continue to stir 2h; After reaction is finished, with the gained suspension filtered, and with distilled water washing, oven dry, thereby obtain the coated with silica silicon powder particle.
B. make carbon coating layer at silicon powder surface and form the composite material that carbon coats silicon.
Weigh 0.2 gram polyvinyl alcohol and be dissolved in 30mL ethanol and the 30mL distilled water, add 1 gram coated with silica silicon powder particle, ultrasonic dispersion 30min; Get the compound of thickness after stirring evaporation then, the drying; It is changed in the porcelain boat, be warmed up to 600 ℃ under nitrogen protection, and be incubated 10 hours, take out the cooling back, obtains the composite material that carbon coats silicon.
C. the composite material that carbon is coated silicon joins the mixed liquor of 100mL NaOH and continuous stirring 60h; Then the gained suspended matter is filtered, and fully wash, dry, thereby obtain the negative material that carbon coats silicon, promptly obtain the composite negative pole material that hollow carbon sphere coats silicon with distilled water.
Lithium ion battery negative material and conductive agent acetylene black, binding agent PVDF (Kynoar) that the foregoing description is obtained are mixed into mixture according to mass ratio at 8: 1: 1, use NMP (1-Methyl-2-Pyrrolidone) that this mixture is modulated into slurry again, and evenly be coated on the Copper Foil, dry in 100 ℃ of vacuum environments then, make the lithium ion battery negative plate.With the lithium sheet is to electrode, and electrolyte is 1mol/LLiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, it is the battery diaphragm of celgard2400 that barrier film adopts model, is assembled into CR2025 type button cell in being full of the glove box of argon gas atmosphere.
The manufacture method of lithium ion battery negative material provided by the invention is simple, and flow process is short, only need three steps can obtain lithium ion battery negative material, so this manufacture method is easy to industrialization.In addition, the lithium ion battery negative material that obtains by the manufacture method of lithium ion battery negative material provided by the invention since the external diameter of centrophyten less than the internal diameter of housing, the cushion space that promptly provides centrophyten to expand in the inside of housing, and housing 2 is limited in centrophyten 1 in the housing 2, thereby can alleviate even eliminate the defective of the housing powder of detached that the volumetric expansion because of centrophyten causes, and then can alleviate the capacity attenuation of lithium ion battery, improve its cycle performance.
The cycle performance collection of illustrative plates of lithium ion battery under constant current 0.1C that Fig. 4 obtains for the lithium ion battery negative material manufacture method that adopts the embodiment of the invention one to propose.Among the figure, abscissa is represented cycle-index, and unit is " inferior "; Ordinate is represented specific capacity, and unit is " mAh/g ".See also Fig. 4, the lithium ion battery first discharge specific capacity has reached 852mAh/g, and after circulation 110 times, the specific capacity of lithium ion battery still is stabilized in 500～600mAh/g.
Need to prove that the cycle performance collection of illustrative plates of lithium ion battery under constant current 0.1C that embodiment two to embodiment four described lithium ion battery negative material manufacture methods obtain is similar substantially to Fig. 4.
The cycle performance collection of illustrative plates of lithium ion battery under constant current 0.1C that Fig. 5 obtains for the lithium ion battery negative material manufacture method that adopts the embodiment of the invention five to propose.Among the figure, abscissa is represented cycle-index, and unit is " inferior "; Ordinate is represented specific capacity, and unit is " mAh/g ".See also Fig. 5, the lithium ion battery first discharge specific capacity has reached 765mAh/g, and after circulation 15 times, the specific capacity of lithium ion battery tends towards stability, and after circulation 20 times, specific capacity is 615mAh/g.
Need to prove that the cycle performance collection of illustrative plates of lithium ion battery under constant current 0.1C that embodiment six to embodiment eight described lithium ion battery negative material manufacture methods obtain is similar substantially to Fig. 5.
Hence one can see that, and the lithium ion battery negative material that is obtained by the manufacture method of lithium ion battery negative material provided by the invention has improved the cycle performance of lithium ion battery.
Fig. 6 is XRD (X-ray diffraction) collection of illustrative plates of lithium ion battery negative material provided by the invention.Among the figure, abscissa is represented the angle of diffraction, unit be " ° "; Ordinate is represented diffracted intensity, unit: atomic unit a.u..As can be seen from Figure 6, have only the diffraction maximum of Si in the negative material, the diffraction maximum of carbon do not occur, this shows that the carbon in the carbon-silicon composite material is amorphous carbon.
Present embodiment also provides a kind of lithium ion battery, comprises negative pole, and the lithium ion battery negative material that this negative pole adopts present embodiment to provide is made.Because lithium ion battery negative material has the space of volumetric expansion, and still is constrained on after the expansion of silicon volume in the housing, this can alleviate the volumetric expansion of charge and discharge process effectively, thereby alleviates even elimination electroactive material powder of detached phenomenon.Therefore, the lithium ion battery that provides of present embodiment has excellent cycle performance.
Be understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement also are considered as protection scope of the present invention.
Claims (25)
1. lithium ion battery negative material, the housing that comprises centrophyten and coat described centrophyten is characterized in that, the external diameter of described centrophyten is less than the internal diameter of described housing.
2. lithium ion battery negative material according to claim 1 is characterized in that, described centrophyten is silicon powder particle or coated with silica silicon powder particle.
3. lithium ion battery negative material according to claim 1 is characterized in that, the particle diameter of described centrophyten is 0.05～5 μ m.
4. lithium ion battery negative material according to claim 1 is characterized in that, described housing is the carbon coating layer of porous.
5. the manufacture method of a lithium ion battery negative material is characterized in that, may further comprise the steps:
Step s10 obtains centrophyten;
Step s20 makes coating layer on the surface of described centrophyten, thereby forms composite material;
Step s30 reduces the outside dimension of described centrophyten, thereby forms the housing of internal diameter greater than described centrophyten external diameter in the periphery of described centrophyten.
6. manufacture method according to claim 5 is characterized in that, described coating layer is a carbon coating layer.
7. manufacture method according to claim 6 is characterized in that, described carbon coating layer obtains by following steps:
Carbon precursor polymer and solvent are mixed with carbon precursor polymer solution;
Described centrophyten is added described carbon precursor polymer solution and forms carbon precursor polymer suspension-turbid liquid;
Make the solvent evaporation in the described carbon precursor polymer suspension-turbid liquid, thereby obtain the centrophyten of carbon precursor polymer overmold;
Make the carbonization of described carbon precursor polymer, obtain described carbon coating layer, thereby form composite material with surface at described centrophyten;
Perhaps, carbon precursor polymer is mixed with described centrophyten ball milling, so that the described centrophyten of carbon precursor polymer overmold;
Make the carbonization of described carbon precursor polymer, obtain described carbon coating layer, thereby form composite material with surface at described centrophyten.
8. manufacture method according to claim 7, it is characterized in that described carbon precursor polymer is a kind of or wherein several mixture in polyvinyl alcohol, butadiene-styrene rubber breast, sodium carboxymethylcellulose, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, phenolic resins, pitch, epoxy resin, glucose, sucrose, cellulose, the starch.
9. manufacture method according to claim 7 is characterized in that, the carbonization in inert atmosphere of described carbon precursor polymer, and carburizing temperature is 400～1200, carbonization time is 0.1～12 hour.
10. manufacture method according to claim 9 is characterized in that, described inert atmosphere is the mist of nitrogen, argon gas or argon gas and hydrogen.
11. manufacture method according to claim 7 is characterized in that, described centrophyten is a silica flour, reduces the outside dimension of described centrophyten with forms of corrosion by corrosive liquid.
12. manufacture method according to claim 11, it is characterized in that described corrosive liquid is hydrofluoric acid and the formulated corrosive liquid of hydrogen peroxide, in described corrosive liquid, the mass concentration of described hydrofluoric acid is 3%～20%, and the mass concentration of described hydrogen peroxide is 1%～15%; Perhaps,
Described corrosive liquid is the corrosive liquid that hydrofluoric acid and nitric acid system form, and in described corrosive liquid, the mass concentration of described hydrofluoric acid is 3%～40%, and the mass concentration of described nitric acid is 5%～35%; Perhaps,
Described corrosive liquid is an inorganic base, and the mass concentration of described inorganic base is 0.4%～30%.
13. manufacture method according to claim 5 is characterized in that, described centrophyten is the coated with silica silicon powder particle, reduces the outside dimension of described centrophyten with forms of corrosion by corrosive liquid.
14. manufacture method according to claim 13 is characterized in that, described corrosive liquid is hydrofluoric acid and the formulated corrosive liquid of hydrogen peroxide, and the mass concentration of described hydrofluoric acid is 3%～20%, and the mass concentration of described hydrogen peroxide is 1%～15%; Perhaps,
Described corrosive liquid is the corrosive liquid that hydrofluoric acid and nitric acid system form, and the mass concentration of described hydrofluoric acid is 3%～40%, and the mass concentration of described nitric acid is 5%～35%; Perhaps,
Described corrosive liquid is an inorganic base, and the mass concentration of described inorganic base is 0.4%～30%; Perhaps,
Described corrosive liquid is a hydrofluoric acid solution, and its mass concentration is 3%～40%.
15., it is characterized in that described corrosive liquid is hydrofluoric acid and the formulated corrosive liquid of hydrogen peroxide according to claim 12 or 14 described manufacture methods, the mass concentration of described hydrofluoric acid is 3%～15%, the mass concentration of described hydrogen peroxide is 3%～10%.
16., it is characterized in that described corrosive liquid is the corrosive liquid that hydrofluoric acid and nitric acid system form according to claim 12 or 14 described manufacture methods, the mass concentration of described hydrofluoric acid is 3%～15%, the mass concentration of described nitric acid is 5%～15%.
17., it is characterized in that described inorganic base is NaOH or potassium hydroxide or sodium carbonate according to claim 12 or 14 described manufacture methods.
18. manufacture method according to claim 7 is characterized in that, the mass ratio of described composite material and described corrosive liquid is 1: 10～1: 1000, and etching time is 0.5～100 hour.
19. manufacture method according to claim 18 is characterized in that, the mass ratio of described composite material and described corrosive liquid is 1: 10～1: 50, and etching time is 2～10 hours.
20., it is characterized in that the mass ratio of described carbon precursor polymer and described centrophyten is 1: 20～2: 1 according to claim 11 or 13 described manufacture methods.
21. manufacture method according to claim 13 is characterized in that, described coated with silica silicon powder particle obtains in the following manner:
Silica flour is scattered in the ethanolic solution to obtain silica flour suspension;
Tetraethoxysilane is mixed the acquisition mixed liquor with ethanol;
Described mixed liquor is added in the described silica flour suspension;
Add catalyst and make described tetraethoxysilane generation hydrolysis, thereby obtain the coated with silica silicon powder particle.
22. manufacture method according to claim 21 is characterized in that, tetraethoxysilane is mixed with ethanol in the step that obtains mixed liquor, the volume ratio of described tetraethoxysilane and ethanol is 1: 1～1: 2.
23. manufacture method according to claim 21, it is characterized in that, described mixed liquor is being added in the step of described silica flour suspension, the addition of described mixed liquor added according to the mol ratio of silicon in silicon in the tetraethoxysilane and the described silica flour suspension in 3: 1～1: 1.
24. manufacture method according to claim 21 is characterized in that, described catalyst is the acid of 0.1～2mol/L or the alkali of 0.05～1mol/L.
25. a lithium ion battery comprises negative pole, it is characterized in that, described negative pole adopts any described lithium ion battery negative material of claim 1-4 to make.
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