CN102881883B - Ternary composite cathode material of lithium battery and preparation method of ternary composite cathode material - Google Patents
Ternary composite cathode material of lithium battery and preparation method of ternary composite cathode material Download PDFInfo
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- CN102881883B CN102881883B CN201210394509.XA CN201210394509A CN102881883B CN 102881883 B CN102881883 B CN 102881883B CN 201210394509 A CN201210394509 A CN 201210394509A CN 102881883 B CN102881883 B CN 102881883B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 158
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000010406 cathode material Substances 0.000 title abstract description 14
- 239000011206 ternary composite Substances 0.000 title abstract 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 119
- 239000010936 titanium Substances 0.000 claims abstract description 77
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 77
- 229920002472 Starch Polymers 0.000 claims abstract description 58
- 235000019698 starch Nutrition 0.000 claims abstract description 58
- 239000008107 starch Substances 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 55
- 239000010439 graphite Substances 0.000 claims abstract description 55
- 239000002131 composite material Substances 0.000 claims abstract description 48
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 9
- 150000003608 titanium Chemical class 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 86
- 239000003610 charcoal Substances 0.000 claims description 33
- 239000011812 mixed powder Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000011268 mixed slurry Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 15
- 238000000713 high-energy ball milling Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000007833 carbon precursor Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 30
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000002427 irreversible effect Effects 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 44
- 239000003792 electrolyte Substances 0.000 description 30
- 230000004888 barrier function Effects 0.000 description 21
- 239000000203 mixture Substances 0.000 description 16
- 239000012528 membrane Substances 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 230000009977 dual effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 9
- 239000005030 aluminium foil Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 229910013870 LiPF 6 Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000003475 lamination Methods 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000004513 sizing Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 244000103152 Eleocharis tuberosa Species 0.000 description 1
- 235000014309 Eleocharis tuberosa Nutrition 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910015014 LiNiCoAlO Inorganic materials 0.000 description 1
- 229910013210 LiNiMnCoO Inorganic materials 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 235000002098 Vicia faba var. major Nutrition 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- USEGOPGXFRQEMV-UHFFFAOYSA-N fluoro hypofluorite titanium Chemical compound [Ti].FOF USEGOPGXFRQEMV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- -1 graphite compound Chemical class 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a ternary composite cathode material of a lithium battery and a preparation method of the ternary composite cathode material, and belongs to the technical field of cathode materials of lithium batteries. The ternary composite cathode material of the lithium battery, provided by the invention, is prepared from the titanium oxides, titanium salts or titanium elementary substances used as a titanium source, lithium salts used as a lithium source, starch used as a precursor of hard carbon and expanded graphite; and the ternary composite cathode material of the lithium battery comprises the following components in parts by weight: 50-98 parts of hard carbon, 1.5-45 parts of lithium titanate and 0.5-5 parts of expanded graphite. The composite cathode material disclosed by the invention has the advantages of large specific capacity, high first efficiency, favorable multiplying power and low-temperature performances, low irreversible capacity, high safety and long circulating life and meets the requirement of a novel lithium ion battery pair.
Description
Technical field
The present invention relates to negative material of a kind of lithium battery and preparation method thereof, more particularly, the present invention relates to a kind of lithium battery tertiary composite negative pole material and preparation method thereof, belong to lithium cell cathode material technical field.
Background technology
Lithium rechargeable battery (referred to as lithium battery) has the advantages such as energy density is large, operating voltage is high, have extended cycle life, pollution-free, security performance is good.Based on these advantages, lithium battery is with a wide range of applications in the many-side such as portable electric appts, electric automobile, extensive energy storage, space technology, national defense industry.
The research of lithium cell cathode material is one of key technology of lithium ion battery always.In general, lithium cell cathode material is divided into charcoal negative pole and the large class of non-charcoal negative pole two.Wherein, carbon cathode material especially graphite carbon negative material causes worldwide extensive research and development with the structural stability of its height and good cycle performance, becomes the lithium ion battery negative material occupying mainstream market at present.But the capacity of its 372mAh/g is too low, the requirement of market development more and more can not be met.And there is layer structure due to graphite, therefore when in the gap that lithium ion enters layer and layer, graphite volumetric expansion about 10% will be made.If charge rate is too fast, effect is too violent, will cause peeling off of graphite, even short circuit blast.Why charge rate is slow for general commercial battery, is exactly mainly in order to avoid this danger.Therefore, people's diversion on other material, such as soft charcoal, hard charcoal, charcoal/silicon composite, metal oxide etc.With regard to existing market, in Novel anode material, hard charcoal and lithium titanate have achieved the commercial application of certain scale, and other material overcomes not yet well due to the defect of self, is mostly also in laboratory development.
Though hard charcoal is through high-temperature process, graphite network plane still undeveloped (
lclittle), the stacking number of plies few (
lalittle), arrangement disorder (
d 002 greatly), micropore is many, and the storage for lithium provides good place.The higher capacity that hard charcoal has with its random sequence, low cost and excellent cycle performance cause the great interest of people.Sony company obtains by thermal depolymerization furfuryl alcohol the Carbon Materials that specific capacity is 450mAh/g; Kanebo company makes the pyrolytic carbon negative material of presoma reversible capacity with polyphenyl phenol reaches 580mAh/g, the embedding lithium capacity of the theory far beyond graphite carbon material 372mAh/g, thus makes people carry out a large amount of research and development to it.We disclose with natural polymer in previous patent (application number is respectively 201110360282.2 and 201110360267.8) is the hard carbon cathode material of raw material.This several hard carbon material capacity reaches more than 500mAh/g, and high rate performance and cryogenic property are all better than conventional graphite negative pole.But because the defect of hard carbon material own is more, although so through modification, generally its irreversible capacity is all higher than 10%.And the charge and discharge platform of hard carbon material closely lithium metal own, in charging process, easily there is lithium separate out, and then battery is short-circuited danger.These hinder hard carbon material large-scale commercial on lithium ion battery and use.
Lithium titanate (chemical formula Li4Ti5O12) is a kind of lithium cell cathode material newly developed in recent years.Lithium titanate is 1.55V relative to the current potential of lithium electrode, and far above graphite and hard carbon material, therefore the efficiency first of lithium titanate anode is higher than 95%, and lithium metal precipitation also can not occur in charge and discharge process, can improve the security performance of battery.In addition, embed at Li or deviate from process, crystal formation does not change, change in volume is less than 1%, and be therefore called as " zero strain material ", this is significant, can avoid causing structural damage due to the flexible back and forth of electrode material in charge and discharge cycles, thus improve cycle performance and the useful life of electrode, decrease and increase with cycle-index and bring specific capacity significantly to decay, make lithium titanate have more excellent cycle performance.But lithium titanate theoretical specific capacity is 175mAh/g, actual specific capacity 150 ~ 160mAh/g, far below carbon class negative material, the demand of lithium battery high-energy-density can not be met.The conductivity of lithium titanate is also lower, is unfavorable for the application of battery high rate charge-discharge.
It is 201110072854.7 that State Intellectual Property Office discloses an application number in 2011.8.17, name is called the patent of invention of " filling high-power winding column type lithium ion battery soon ", this disclosure of the invention one fills high-power winding column type lithium ion battery soon, comprise anode pole piece, cathode pole piece, porous isolating membrane, winding becomes pillar core body successively, and at core extracorporeal set metal shell, electrolyte is noted in metal shell, it is characterized in that: positive electrode is cobalt acid lithium, LiMn2O4, element material, nickel cobalt lithium aluminate, LiFePO 4, lithium vanadate wherein one or more, negative material is one or more in graphite, lithium titanate.Plus plate current-collecting body is thickness at the preliminary treatment aluminium foil of 8 ~ 30 microns or aluminium net; Negative current collector be thickness 8 ~ 30 microns Copper Foil, copper mesh, iron nickel plating paper tinsel or iron nickel plating net.Electrolyte in electrolyte is lithium hexafluoro phosphate, the one of biethyl diacid lithium borate or two kinds mix; Solvent in electrolyte is two kinds or several mixing of EC, PC, DMC, DEC, EA etc.The present invention can realize battery high-power output also can realize filling soon of battery, and security performance is high.
In above-mentioned patent, negative pole uses one or more of graphite, lithium titanate, and from aforementioned discussion, the capacity of graphite and lithium titanate all has limitation, is respectively 372mAh/g and 175mAh/g, makes the energy density of battery be subject to certain restriction.And this patent just by graphite and lithium titanate used in combination, and at micro-scale, the two is not carried out compound, the shortcoming of graphite electrolyte poor compatibility and cyclicity difference is covered by the advantage that therefore could not make full use of lithium titanate high efficiency and excellent cycle first.
Summary of the invention
The present invention is intended to solve hard carbon material in above-mentioned prior art, and efficiency is low first, easily analyse lithium, lithium titanate material capacity is low, the problem that conductivity is low, provides a kind of lithium battery tertiary negative material, it is large that this material has specific capacity, efficiency is high first, high rate performance and cryogenic property excellent, irreversible capacity is low, fail safe and the good advantage of cycle life, agreed with the demand that new type lithium ion battery is right.
Another object of the present invention is to provide a kind of preparation method of above-mentioned lithium battery tertiary negative material, its objective is and uses simple technique and cheap cost to obtain high performance tri compound negative material.
In order to realize foregoing invention object, concrete technical scheme of the present invention is as follows:
A kind of lithium battery tertiary composite negative pole material, it is characterized in that: described lithium battery tertiary composite negative pole material is: by as the titanyl compound in titanium source, titanium salt or titanium simple substance, lithium salts as lithium source, the starch as hard carbon precursor and expanded graphite are made, and comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
Hard charcoal 50 ~ 98 parts
Lithium titanate 1.5 ~ 45 parts
Expanded graphite 0.5 ~ 5.0 part.
Titanyl compound of the present invention, titanium salt or titanium simple substance are this area conventional articles for use, such as titanium tetrachloride, butyl titanate, isopropyl titanate, titanium sulfate, titanyl sulfate, difluoro oxygen titanium, metal titanium sheet etc.
Lithium salts of the present invention is the lithium hydroxide, lithium oxalate, lithium acetate, lithium carbonate, lithia, lithium sulfate, lithium nitrate, lithium chloride etc. of this area routine.
The preferred lithium carbonate of above-mentioned lithium salts.
Lithium battery tertiary composite negative pole material in above-mentioned basic technical scheme adopts conventional negative material preparation technology can realize first goal of the invention of the present invention.
In order to realize another goal of the invention of the present invention, preferably provide a kind of preparation technology simpler and with low cost below:
A preparation method for lithium battery tertiary composite negative pole material, is characterized in that: comprise following processing step:
A, take lithium source and titanium source by elemental lithium and titanium elements atomic ratio 3:5 ~ 5:5, then take starch according to starch and titanium source quality than 10:1 ~ 100:1, by three kinds of raw material Homogeneous phase mixing, obtain the mixed-powder of lithium source, titanium source and starch;
The mixed-powder of B, lithium source according to obtaining in steps A, titanium source and starch takes deionized water, ethanol or acetone as dispersant with liquid quality than for 1:10 ~ 1:100, the mixed-powder of dispersant and the lithium source obtained in steps A, titanium source and starch is mixed, obtains mixed slurry;
C, by mixed slurry stir 1 ~ 10 hour, by dispersant dry, obtain dry powder;
D, get dry powder put into heating furnace, rise to 600 ~ 1000 DEG C with the heating rate of 0.1 ~ 1 DEG C/min under an inert atmosphere, heat treated 0.2 ~ 5h, is then cooled to room temperature under an inert atmosphere, obtain cool powder;
E, the ratio of cooling powder and expanded graphite 10:1 ~ 100:1 in mass ratio to be mixed, join in the solvent of 10 ~ 20 times of volumes, stir or ultrasonic vibration 0.5 ~ 5h, then with centrifugal, filter or the mode of suction filtration by solid and separated from solvent, then in drying box, solvent is dried, namely obtain hard charcoal/lithium titanate/expanded graphite tri compound negative material.
In step, the described lithium source that takes and titanium source are for being that 4:5 takes according to elemental lithium and titanium elements atomic ratio.
In step, described titanium source particle diameter is 10 ~ 1000nm of this area routine, and preferable particle size is 50nm.
In step, described starch is the cereal starch (as rice starch, cornstarch, sorghum starch, wheaten starch etc.) of this area routine, potato starch (as tapioca, sweet potato starch, farina etc.), one among bean starch (as green starch, Faba bean starch, pea starch etc.) and/or other kind of starch (as Tapioca starch, lotus root starch, Chinese Water Chestnut Starch, acorn starch), or several arbitrary proportion mixtures.
In stepb, the mixed-powder of described lithium source, titanium source and starch with liquid quality than being 1:20.
In step C, described being stirred by mixed slurry refers to and enters high-energy ball milling, ball milling 1 ~ 10 hour for 1 ~ 10 hour.
Above-mentioned high-energy ball milling is conventional planetary ball mill or sand mill, and rotating speed is 300 ~ 1000r/min, preferably 800 r/min.
In step D, described heating furnace is conventional tube furnace, box type furnace or rotary furnace, preferred rotary furnace.
In step D, described inert atmosphere is conventional nitrogen atmosphere, argon gas atmosphere or helium atmosphere, preferred nitrogen atmosphere.
In step e, described expanded graphite is adopt the obtained conventional products of techniques well known or directly buy.
In step e, described solvent is conventional water, ethanol, acetone, toluene, n-hexane, cyclohexane, benzene or dimethylbenzene, preferred alcohol.
Refer at 20 ~ 80 DEG C of temperature in the stirring described in step e, carry out stirring 1 ~ 4h with rotating speed 100 ~ 1500r/min.
According to the problem mentioned in background technology, and the situation of prior art development, for these reasons, this invention exploits a kind of spherical hard charcoal/lithium titanate/expanded graphite tri compound negative material, the height ratio capacity of the hard charcoal of this materials combine and high-rate characteristics, high efficiency, fail safe and the cycle life first of lithium titanate, and the good electric conductivity of graphite.Therefore, this composite negative pole material has that specific capacity is large, and efficiency is high first, high rate performance and cryogenic property excellent, irreversible capacity is low, and fail safe and the good advantage of cycle life, agreed with the demand that new type lithium ion battery is right.
In the present invention, we use capacity higher (can higher than 400mAh/g), and electrolyte compatibility is good, and the excellent spherical hard charcoal of high rate performance, as material core, uses lithium titanate by coated for hard charcoal, and such lithium titanate directly and electrolyte contacts.In order to improve material electric conductivity and multiplying power property further, again by the expanded graphite compound of spherical hard charcoal/lithium titanate and excellent electric conductivity, using expanded graphite as space conductive network.The spherical hard charcoal/lithium titanate/expanded graphite tri compound negative material obtained like this, has had both height ratio capacity and the high-rate characteristics of hard charcoal, high efficiency, fail safe and the cycle life first of lithium titanate, and the good electric conductivity of graphite.Therefore, this composite negative pole material has that specific capacity is large, and efficiency is high first, high rate performance and cryogenic property excellent, irreversible capacity is low, and fail safe and the good advantage of cycle life, agreed with the demand that new type lithium ion battery is right.
Present invention offers following Advantageous Effects:
1, the low in raw material price used of this method, abundance, is easy to realize large-scale industrial and produces; The present invention utilizes the intrinsic pattern of starch material, without the need to through special balling technique, spherical compound, technique and equipment simple, energy consumption is low; Composite material prepared by the present invention, based on hard charcoal, therefore possesses the height ratio capacity of hard charcoal and high-rate characteristics and good cryogenic property; Lithium titanate is coated on the skin of hard charcoal by composite material prepared by the present invention, therefore has high efficiency, fail safe and the cycle life first of lithium titanate; Composite material prepared by the present invention has the three-dimensional conductive network that expanded graphite is formed, the conduction of building as electronics of solid space network configuration is utilized to provide good passage, thus improve the voltage delay effect of hard carbon material, also overcome the defect of the low electronic conductivity of lithium titanate material; Composite negative pole material disclosed by the invention has that specific capacity is large, and efficiency is high first, high rate performance and cryogenic property excellent, irreversible capacity is low, and fail safe and the good advantage of cycle life, agreed with the demand that new type lithium ion battery is right.
2, the preferred lithium carbonate in lithium source in ternary anode material of the present invention, makes cheap, reduces while old, can be obtained by reacting the lithium titanate of function admirable.
3, preparation method of the present invention, in step, is preferably that 4:5 takes lithium source and titanium source according to elemental lithium and titanium elements atomic ratio, is beneficial to and obtains pure lithium titanate, improve the quality of final product; Nano level titanium source makes the lithium titanate particle diameter obtained also be nanoscale, and lithium ion mobility path is short, is beneficial to raising battery performance, and preferably 50nm is a most suitable particle diameter, is also easy to directly buy obtain, and reduces old, improves production efficiency.
4, preparation method of the present invention, in stepb, the mixed-powder of described lithium source, titanium source and starch and liquid quality are than preferably 1:20, the composite material charcoal obtained like this accounts for about 80% greatly, lithium titanate accounts for about 15%, both ensure that the hard charcoal proportion of high power capacity was high, and ensured that again covered effect is good, make material property excellent.
5, preparation method of the present invention, in step C, the preferred high-energy ball milling of described stirring, make mixing dispersion evenly; In addition, rotating speed is too low is unfavorable for that mixing is fully, rotating speed too high to equipment and horsepower requirements high, and may destroy sphericity, preferred rotating speed is 800 r/min, can ensure that material fully contacts mixing, ensures that again starch spheric granules destructiveness is low.
6, preparation method of the present invention, in step D, the preferred rotary furnace of its heating furnace, can make heating material even, make material consistency better; Inert gas preferred nitrogen in step D, in step e, solvent preferred alcohol can ensure economy, reduces production cost, and can ensure the quality of final product simultaneously.
Accompanying drawing explanation
Fig. 1 is the structural representation of lithium battery tertiary composite negative pole material of the present invention.
Embodiment
embodiment 1
A kind of lithium battery tertiary composite negative pole material, it is characterized in that: described lithium battery tertiary composite negative pole material is: by as the titanyl compound in titanium source, titanium salt or titanium simple substance, lithium salts as lithium source, the starch as hard carbon precursor and expanded graphite are made, and comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
Hard charcoal 50 parts
Lithium titanate 1.5 parts
Expanded graphite 0.5 part.
Preferred: described lithium salts is lithium carbonate.
embodiment 2
A kind of lithium battery tertiary composite negative pole material, it is characterized in that: described lithium battery tertiary composite negative pole material is: by as the titanyl compound in titanium source, titanium salt or titanium simple substance, lithium salts as lithium source, the starch as hard carbon precursor and expanded graphite are made, and comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
Hard charcoal 98 parts
Lithium titanate 45 parts
Expanded graphite 5 parts.
Preferred: described lithium salts is lithium carbonate.
embodiment 3
A kind of lithium battery tertiary composite negative pole material, it is characterized in that: described lithium battery tertiary composite negative pole material is: by as the titanyl compound in titanium source, titanium salt or titanium simple substance, lithium salts as lithium source, the starch as hard carbon precursor and expanded graphite are made, and comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
Hard charcoal 74 parts
Lithium titanate 23.25 parts
Expanded graphite 2.75 parts.
Preferred: described lithium salts is lithium carbonate.
embodiment 4
A kind of lithium battery tertiary composite negative pole material, it is characterized in that: described lithium battery tertiary composite negative pole material is: by as the titanyl compound in titanium source, titanium salt or titanium simple substance, lithium salts as lithium source, the starch as hard carbon precursor and expanded graphite are made, and comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
Hard charcoal 60 parts
Lithium titanate 41 parts
Expanded graphite 1.2 parts.
Preferred: described lithium salts is lithium carbonate.
embodiment 5
A preparation method for lithium battery tertiary composite negative pole material, comprises following processing step:
A, take lithium source and titanium source by elemental lithium and titanium elements atomic ratio 3:5, then take starch according to starch and titanium source quality than 10:1, by three kinds of raw material Homogeneous phase mixing, obtain the mixed-powder of lithium source, titanium source and starch;
The mixed-powder of B, lithium source according to obtaining in steps A, titanium source and starch takes deionized water, ethanol or acetone as dispersant with liquid quality than for 1:10, the mixed-powder of dispersant and the lithium source obtained in steps A, titanium source and starch is mixed, obtains mixed slurry;
C, mixed slurry is stirred 1 hour, dispersant is dried, obtain drying powder;
D, get dry powder put into heating furnace, rise to 600 DEG C with the heating rate of 0.1 DEG C/min under an inert atmosphere, heat treated 0.2h, be then cooled to room temperature under an inert atmosphere, obtain cool powder;
E, the ratio of cooling powder and expanded graphite 10:1 in mass ratio to be mixed, join in the solvent of 10 times of volumes, stir or ultrasonic vibration 0.5h, then with centrifugal, filter or the mode of suction filtration by solid and separated from solvent, then in drying box, solvent is dried, namely obtain hard charcoal/lithium titanate/expanded graphite tri compound negative material.
embodiment 6
A preparation method for lithium battery tertiary composite negative pole material, comprises following processing step:
A, take lithium source and titanium source by elemental lithium and titanium elements atomic ratio 5:5, then take starch according to starch and titanium source quality than 100:1, by three kinds of raw material Homogeneous phase mixing, obtain the mixed-powder of lithium source, titanium source and starch;
The mixed-powder of B, lithium source according to obtaining in steps A, titanium source and starch takes deionized water, ethanol or acetone as dispersant with liquid quality than for 1:100, the mixed-powder of dispersant and the lithium source obtained in steps A, titanium source and starch is mixed, obtains mixed slurry;
C, mixed slurry is stirred 10 hours, dispersant is dried, obtain drying powder;
D, get dry powder put into heating furnace, rise to 1000 DEG C with the heating rate of 1 DEG C/min under an inert atmosphere, heat treated 5h, be then cooled to room temperature under an inert atmosphere, obtain cool powder;
E, the ratio of cooling powder and expanded graphite 100:1 in mass ratio to be mixed, join in the solvent of 20 times of volumes, stir or ultrasonic vibration 5h, then with centrifugal, filter or the mode of suction filtration by solid and separated from solvent, then in drying box, solvent is dried, namely obtain hard charcoal/lithium titanate/expanded graphite tri compound negative material.
embodiment 7
A preparation method for lithium battery tertiary composite negative pole material, comprises following processing step:
A, take lithium source and titanium source by elemental lithium and titanium elements atomic ratio 4:5, then take starch according to starch and titanium source quality than 55:1, by three kinds of raw material Homogeneous phase mixing, obtain the mixed-powder of lithium source, titanium source and starch;
The mixed-powder of B, lithium source according to obtaining in steps A, titanium source and starch takes deionized water, ethanol or acetone as dispersant with liquid quality than for 1:55, the mixed-powder of dispersant and the lithium source obtained in steps A, titanium source and starch is mixed, obtains mixed slurry;
C, mixed slurry is stirred 5.5 hours, dispersant is dried, obtain drying powder;
D, get dry powder put into heating furnace, rise to 800 DEG C with the heating rate of 0.55 DEG C/min under an inert atmosphere, heat treated 2.6h, be then cooled to room temperature under an inert atmosphere, obtain cool powder;
E, the ratio of cooling powder and expanded graphite 55:1 in mass ratio to be mixed, join in the solvent of 15 times of volumes, stir or ultrasonic vibration 2.75h, then with centrifugal, filter or the mode of suction filtration by solid and separated from solvent, then in drying box, solvent is dried, namely obtain hard charcoal/lithium titanate/expanded graphite tri compound negative material.
embodiment 8
A preparation method for lithium battery tertiary composite negative pole material, comprises following processing step:
A, take lithium source and titanium source by elemental lithium and titanium elements atomic ratio 3.6:5, then take starch according to starch and titanium source quality than 88:1, by three kinds of raw material Homogeneous phase mixing, obtain the mixed-powder of lithium source, titanium source and starch;
The mixed-powder of B, lithium source according to obtaining in steps A, titanium source and starch takes deionized water, ethanol or acetone as dispersant with liquid quality than for 1:21, the mixed-powder of dispersant and the lithium source obtained in steps A, titanium source and starch is mixed, obtains mixed slurry;
C, mixed slurry is stirred 3 hours, dispersant is dried, obtain drying powder;
D, get dry powder put into heating furnace, rise to 950 DEG C with the heating rate of 0.27 DEG C/min under an inert atmosphere, heat treated 0.9h, be then cooled to room temperature under an inert atmosphere, obtain cool powder;
E, the ratio of cooling powder and expanded graphite 36:1 in mass ratio to be mixed, join in the solvent of 18 times of volumes, stir or ultrasonic vibration 3.5h, then with centrifugal, filter or the mode of suction filtration by solid and separated from solvent, then in drying box, solvent is dried, namely obtain hard charcoal/lithium titanate/expanded graphite tri compound negative material.
embodiment 9
On the basis of embodiment 5 ~ 8, preferably:
In step, the described lithium source that takes and titanium source are for being that 4:5 takes according to elemental lithium and titanium elements atomic ratio.
In step, described titanium source particle diameter is 50nm.
In stepb, the mixed-powder of described lithium source, titanium source and starch with liquid quality than being 1:20.
In step C, described being stirred by mixed slurry refers to and enters high-energy ball milling for 1 hour, ball milling 1 hour.
Described high-energy ball milling is conventional planetary ball mill or sand mill, and rotating speed is 800 r/min.
In step D, described heating furnace is rotary furnace.
Refer at 20 DEG C of temperature in the stirring described in step e, carry out stirring 1h with rotating speed 100r/min.
embodiment 10
On the basis of embodiment 5 ~ 8, preferably:
In step, the described lithium source that takes and titanium source are for being that 4:5 takes according to elemental lithium and titanium elements atomic ratio.
In step, described titanium source particle diameter is 50nm.
In stepb, the mixed-powder of described lithium source, titanium source and starch with liquid quality than being 1:20.
In step C, described being stirred by mixed slurry refers to and enters high-energy ball milling for 10 hours, ball milling 10 hours.
Described high-energy ball milling is conventional planetary ball mill or sand mill, and rotating speed is 800 r/min.
In step D, described heating furnace is rotary furnace.
Refer at 80 DEG C of temperature in the stirring described in step e, carry out stirring 4h with rotating speed 1500r/min.
embodiment 11
On the basis of embodiment 5 ~ 8, preferably:
In step, the described lithium source that takes and titanium source are for being that 4:5 takes according to elemental lithium and titanium elements atomic ratio.
In step, described titanium source particle diameter is 50nm.
In stepb, the mixed-powder of described lithium source, titanium source and starch with liquid quality than being 1:20.
In step C, described being stirred by mixed slurry refers to and enters high-energy ball milling for 5.5 hours, ball milling 5.5 hours.
Described high-energy ball milling is conventional planetary ball mill or sand mill, and rotating speed is 800 r/min.
In step D, described heating furnace is rotary furnace.
Refer at 50 DEG C of temperature in the stirring described in step e, carry out stirring 2.5h with rotating speed 800r/min.
embodiment 12
On the basis of embodiment 5 ~ 8, preferably:
In step, the described lithium source that takes and titanium source are for being that 4:5 takes according to elemental lithium and titanium elements atomic ratio.
In step, described titanium source particle diameter is 50nm.
In stepb, the mixed-powder of described lithium source, titanium source and starch with liquid quality than being 1:20.
In step C, described being stirred by mixed slurry refers to and enters high-energy ball milling for 3 hours, ball milling 3 hours.
Described high-energy ball milling is conventional planetary ball mill or sand mill, and rotating speed is 800 r/min.
In step D, described heating furnace is rotary furnace.
Refer at 66 DEG C of temperature in the stirring described in step e, carry out stirring 2h with rotating speed 500r/min.
embodiment 13
The hard charcoal capacity 480mAh/g that the present invention uses, lithium titanate capacity 160mAh/g, after ratio compound of the present invention, capacity is 350-470 mAh/g, far above lithium titanate capacity, also higher than the capacity of graphite cathode.The negative material that the present invention obtains first efficiency is 88-94%, far above about 70% of hard carbon material.After tested, negative material of the present invention can be completely compatible in PC base low-temperature electrolyte, and after 3000 circulations, capability retention is higher than 90%, and does not have to analyse lithium phenomenon.
embodiment 14
A kind of lithium ion battery, comprises battery case, pole piece and electrolyte, and described pole piece and electrolyte sealing are contained in battery case, and described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole.
Positive electrode composition and positive pole: adopt cobalt acid lithium (LiCO
2) as positive active material, the method in common knowledge according to those skilled in the art prepares anode sizing agent; By slurry dual coating on the aluminium foil of 16 microns; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopt the composite material preparing the embodiment 1 ~ 4 that negative material technique prepares in embodiment 5 ~ 8 to be negative electrode active material, the method in common knowledge according to those skilled in the art prepares cathode size; By cathode size dual coating on the Copper Foil of 12 microns, under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Electrolyte: EC DMC EMC=1:1:1(LiPF
6content is 1.0mol/L).
Pole piece: the positive pole prepared with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, obtains in humidity-controlled environment with the order lamination of negative pole/barrier film/positive pole/barrier film/negative pole.
Comparative example 1: adopt said method to prepare lithium ion battery, difference negative material is ordinary graphite.
embodiment 15
A kind of lithium ion battery, comprises battery case, pole piece and electrolyte, and described pole piece and electrolyte sealing are contained in battery case, and described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole.
Positive electrode composition and positive pole: adopt LiMn2O4 (LiMn
2o
4) as positive active material, the method in common knowledge according to those skilled in the art prepares anode sizing agent; By slurry dual coating on the aluminium foil of 16 microns; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopt the composite material preparing the embodiment 1 ~ 4 that negative material technique prepares in embodiment 5 ~ 8 to be negative electrode active material, the method in common knowledge according to those skilled in the art prepares cathode size; By cathode size dual coating on the Copper Foil of 12 microns, under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Electrolyte: EC DMC EMC=1:1:1(LiPF
6content is 1.0mol/L).
Pole piece: the positive pole prepared with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, obtains in humidity-controlled environment with the order lamination of negative pole/barrier film/positive pole/barrier film/negative pole.
Comparative example 2: adopt said method to prepare lithium ion battery, difference negative material is ordinary graphite.
embodiment 16
A kind of lithium ion battery, comprises battery case, pole piece and electrolyte, and described pole piece and electrolyte sealing are contained in battery case, and described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole.
Positive electrode composition and positive pole: adopt ternary material (LiNiMnCoO
2) as positive active material, the method in common knowledge according to those skilled in the art prepares anode sizing agent; By slurry dual coating on the aluminium foil of 16 microns; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopt the composite material preparing the embodiment 1 ~ 4 that negative material technique prepares in embodiment 5 ~ 8 to be negative electrode active material, the method in common knowledge according to those skilled in the art prepares cathode size; By cathode size dual coating on the Copper Foil of 12 microns, under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Electrolyte: EC DMC EMC=1:1:1(LiPF
6content is 1.0mol/L).
Pole piece: the positive pole prepared with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, obtains in humidity-controlled environment with the order lamination of negative pole/barrier film/positive pole/barrier film/negative pole.
Comparative example 3: adopt said method to prepare lithium ion battery, difference negative material is ordinary graphite.
embodiment 17
A kind of lithium ion battery, comprises battery case, pole piece and electrolyte, and described pole piece and electrolyte sealing are contained in battery case, and described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole.
Positive electrode composition and positive pole: adopt ternary material (LiNiCoAlO
2) as positive active material, the method in common knowledge according to those skilled in the art prepares anode sizing agent; By slurry dual coating on the aluminium foil of 16 microns; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopt the composite material preparing the embodiment 1 ~ 4 that negative material technique prepares in embodiment 5 ~ 8 to be negative electrode active material, the method in common knowledge according to those skilled in the art prepares cathode size; By cathode size dual coating on the Copper Foil of 12 microns, under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Electrolyte: EC DMC EMC=1:1:1(LiPF
6content is 1.0mol/L).
Pole piece: the positive pole prepared with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, obtains in humidity-controlled environment with the order lamination of negative pole/barrier film/positive pole/barrier film/negative pole.
Comparative example 4: adopt said method to prepare lithium ion battery, difference negative material is ordinary graphite.
embodiment 18
A kind of lithium ion battery, comprises battery case, pole piece and electrolyte, and described pole piece and electrolyte sealing are contained in battery case, and described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole.
Positive electrode composition and positive pole: adopt LiFePO 4 (LiFePO
4) as positive active material, the method in common knowledge according to those skilled in the art prepares anode sizing agent; By slurry dual coating on the aluminium foil of 16 microns; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopt the composite material preparing the embodiment 1 ~ 4 that negative material technique prepares in embodiment 5 ~ 8 to be negative electrode active material, the method in common knowledge according to those skilled in the art prepares cathode size; By cathode size dual coating on the Copper Foil of 12 microns, under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Electrolyte: EC DMC EMC=1:1:1(LiPF
6content is 1.0mol/L).
Pole piece: the positive pole prepared with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, obtains in humidity-controlled environment with the order lamination of negative pole/barrier film/positive pole/barrier film/negative pole.
Comparative example 5: adopt said method to prepare lithium ion battery, difference negative material is ordinary graphite.
embodiment 19
A kind of lithium ion battery, comprises battery case, pole piece and electrolyte, and described pole piece and electrolyte sealing are contained in battery case, and described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole.
Positive electrode composition and positive pole: adopt LiFePO 4 (LiFePO
4) as positive active material, the method in common knowledge according to those skilled in the art prepares anode sizing agent; By slurry dual coating on the aluminium foil of 16 microns; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopt the composite material preparing the embodiment 1 ~ 4 that negative material technique prepares in embodiment 5 ~ 8 to be negative electrode active material, the method in common knowledge according to those skilled in the art prepares cathode size; By cathode size dual coating on the Copper Foil of 12 microns, under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Electrolyte: PC DMC EMC=1:1:1(LiPF
6content is 1.0mol/L).
Pole piece: the positive pole prepared with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, obtains in humidity-controlled environment with the order lamination of negative pole/barrier film/positive pole/barrier film/negative pole.
Comparative example 6: adopt said method to prepare lithium ion battery, difference negative material is ordinary graphite.
embodiment 20
A kind of lithium ion battery, comprises battery case, pole piece and electrolyte, and described pole piece and electrolyte sealing are contained in battery case, and described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole.
Positive electrode composition and positive pole: adopt LiMn2O4 (LiMn
2o
4) as positive active material, the method in common knowledge according to those skilled in the art prepares anode sizing agent; By slurry dual coating on the aluminium foil of 16 microns; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2.
Cathode composition and negative pole: adopt the composite material preparing the embodiment 1 ~ 4 that negative material technique prepares in embodiment 5 ~ 8 to be negative electrode active material, the method in common knowledge according to those skilled in the art prepares cathode size; By cathode size dual coating on the Copper Foil of 12 microns, under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm
2.
Electrolyte: PC DMC EMC=1:1:1(LiPF
6content is 1.0mol/L).
Pole piece: the positive pole prepared with said method and negative pole, the PE perforated membrane of 20 microns is barrier film, obtains in humidity-controlled environment with the order lamination of negative pole/barrier film/positive pole/barrier film/negative pole.
Comparative example 7: adopt said method to prepare lithium ion battery, difference negative material is ordinary graphite.
embodiment 21
Electrochemical property test
Embodiment 14 ~ 20 and the battery capacity prepared by comparative example 1 ~ 7 are 450mAh(1C).Under room temperature, by embodiment 14 ~ 20 and the obtained lithium ion battery of comparative example 1 ~ 7 with initial charge current density for 0.2mAh/cm
2.Wherein embodiment 14 ~ 17 and the obtained lithium ion battery upper voltage limit 4.2V of comparative example 1 ~ 4, lower voltage limit 3.0V; The lithium ion battery upper voltage limit 3.8V that embodiment 18 ~ 20 and comparative example 5 ~ 7 obtain, lower voltage limit 2.5V.
By the capacity of battery test battery under the large multiplying power of normal temperature 1C, 10C, 0 DEG C of low temperature discharge, normal temperature 1C circulate 1000 conditions, and calculated capacity surplus ratio, as shown in table 1.
Table 1
As can be seen from embodiment 14 ~ 20 and contrast preparation 1 ~ 7, adopt the lithium ion battery of composite negative pole material of the present invention, high rate performance, cryogenic property are excellent, electrolyte compatibility is good, stable cycle performance, comprehensively it seems the lithium battery that various aspects of performance is all far superior to existing graphite cathode and prepares.
Claims (4)
1. a lithium battery tertiary composite negative pole material, it is characterized in that: described lithium battery tertiary composite negative pole material is: by as the titanyl compound in titanium source, titanium salt or titanium simple substance, lithium salts as lithium source, the starch as hard carbon precursor and expanded graphite are made, and comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
Hard charcoal 50 ~ 98 parts
Lithium titanate 1.5 ~ 45 parts
Expanded graphite 0.5 ~ 5 part;
Described lithium battery tertiary composite negative pole material is made up of following processing step:
A, take lithium source and titanium source by elemental lithium and titanium elements atomic ratio 4:5, then take starch according to starch and titanium source quality than 10:1 ~ 100:1, by three kinds of raw material Homogeneous phase mixing, obtain the mixed-powder of lithium source, titanium source and starch; Described titanium source particle diameter is 50nm;
The mixed-powder of B, lithium source according to obtaining in steps A, titanium source and starch takes deionized water, ethanol or acetone as dispersant with liquid quality than for 1:20, the mixed-powder of dispersant and the lithium source obtained in steps A, titanium source and starch is mixed, obtains mixed slurry;
C, mixed slurry is entered high-energy ball milling, ball milling 1 ~ 10 hour, dispersant is dried, obtain drying powder; Described high-energy ball milling rotating speed is 800 r/min;
D, get dry powder put into heating furnace, rise to 600 ~ 1000 DEG C with the heating rate of 0.1 ~ 1 DEG C/min under an inert atmosphere, heat treated 0.2 ~ 5h, is then cooled to room temperature under an inert atmosphere, obtain cool powder;
E, the ratio of cooling powder and expanded graphite 10:1 ~ 100:1 in mass ratio to be mixed, join in the solvent of 10 ~ 20 times of volumes, stir or ultrasonic vibration 0.5 ~ 5h, then with centrifugal, filter or the mode of suction filtration by solid and separated from solvent, then in drying box, solvent is dried, namely obtain hard charcoal/lithium titanate/expanded graphite tri compound negative material.
2. a kind of lithium battery tertiary composite negative pole material according to claim 1, is characterized in that: described lithium salts is lithium carbonate.
3. a kind of lithium battery tertiary composite negative pole material according to claim 1, is characterized in that: in step D, and described heating furnace is rotary furnace.
4. a kind of lithium battery tertiary composite negative pole material according to claim 1, is characterized in that: refer at 20 ~ 80 DEG C of temperature in the stirring described in step e, carry out stirring 1 ~ 4h with rotating speed 100 ~ 1500r/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210394509.XA CN102881883B (en) | 2012-10-17 | 2012-10-17 | Ternary composite cathode material of lithium battery and preparation method of ternary composite cathode material |
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| CN201210394509.XA CN102881883B (en) | 2012-10-17 | 2012-10-17 | Ternary composite cathode material of lithium battery and preparation method of ternary composite cathode material |
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| CN104916825A (en) * | 2015-06-26 | 2015-09-16 | 田东 | Preparation method of lithium battery high-voltage modified cathode material |
| CN105140570B (en) * | 2015-08-06 | 2018-05-04 | 孙杰 | A kind of lithium-ion-power cell group and its manufacture method |
| CN106876675B (en) * | 2017-03-23 | 2019-11-01 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of lithium ion battery lithium titanate composite cathode material of silicon/carbon/graphite |
| CN112242516B (en) * | 2020-10-20 | 2021-07-16 | 湖南长远锂科股份有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN114634203A (en) * | 2022-02-24 | 2022-06-17 | 四川国创成电池材料有限公司 | Lithium ion battery with niobium-titanium-oxygen composite oxide cathode |
| CN115036484A (en) * | 2022-06-24 | 2022-09-09 | 清华大学深圳国际研究生院 | Graphite composite negative electrode material, preparation method thereof and secondary battery |
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