CN102881883A - 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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- CN102881883A CN102881883A CN201210394509XA CN201210394509A CN102881883A CN 102881883 A CN102881883 A CN 102881883A CN 201210394509X A CN201210394509X A CN 201210394509XA CN 201210394509 A CN201210394509 A CN 201210394509A CN 102881883 A CN102881883 A CN 102881883A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 166
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 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 116
- 239000010936 titanium Substances 0.000 claims abstract description 80
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 80
- 229920002472 Starch Polymers 0.000 claims abstract description 59
- 235000019698 starch Nutrition 0.000 claims abstract description 59
- 239000008107 starch Substances 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002131 composite material Substances 0.000 claims abstract description 53
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 51
- 239000010439 graphite Substances 0.000 claims abstract description 51
- 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 92
- 238000005303 weighing Methods 0.000 claims description 31
- 239000003610 charcoal Substances 0.000 claims description 27
- 239000011812 mixed powder Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 18
- 239000011268 mixed slurry Substances 0.000 claims description 18
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- 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 13
- 238000001035 drying Methods 0.000 claims description 12
- 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 7
- 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
- 230000009514 concussion Effects 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
- 238000001914 filtration Methods 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 9
- 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 45
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- 230000000052 comparative effect Effects 0.000 description 11
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- 239000005030 aluminium foil Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
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- 239000007773 negative electrode material Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
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- 229910010707 LiFePO 4 Inorganic materials 0.000 description 5
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- 230000000694 effects Effects 0.000 description 4
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- 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
- 230000002950 deficient 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
- 238000002156 mixing 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
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- 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
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- 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
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004804 winding 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
- 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
- 230000006378 damage Effects 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
- 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
- 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
- 238000009776 industrial production Methods 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
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 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
- 239000000047 product Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- -1 rice starch Polymers 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
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical class [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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 the 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 many-sides 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 non-charcoal negative pole two large classes.Wherein, carbon cathode material especially graphite carbon negative material causes worldwide broad research and exploitation with its structural stability and good cycle performance highly, becomes the lithium ion battery negative material that occupies at present mainstream market.But the capacity of its 372mAh/g is excessively low, more and more can not satisfying the market the requirement of development.And because graphite has layer structure, therefore when lithium ion enter layer with layer the gap in, will make graphite volumetric expansion about 10%.If charge rate is too fast, effect is too violent, will cause peeling off of graphite, even the short circuit blast.Why charge rate is slow for general commercially available battery, is exactly for fear of this danger mainly.Therefore, people's diversion to other material, such as soft charcoal, hard charcoal, charcoal/silicon composite, metal oxide etc.With regard to existing market, hard charcoal and lithium titanate have been realized the commercial application of certain scale in the Novel anode material, and other material also is in the laboratory development mostly because the defective of self overcomes not yet well.
Though hard charcoal is through high-temperature process, the graphite network plane still undeveloped (
LcLittle), the stacking number of plies few (
LaLittle), arrangement disorder (
d 002 Greatly), micropore is many, for the storage of lithium provides good place.Hard charcoal has caused people's very big interest with higher capacity, low cost and the excellent cycle performance that its random ordering was had.Sony company obtains the Carbon Materials that specific capacity is 450mAh/g by the thermal depolymerization furfuryl alcohol; The reversible capacity that Kanebo company makes the pyrolytic carbon negative material of presoma with polyphenyl phenol reaches 580mAh/g, the theoretical embedding lithium capacity 372mAh/g of graphite carbon material head and shoulders above, thus make people carry out a large amount of research and development to it.Hard carbon cathode material take natural polymer as raw material is disclosed in our patent (application number is respectively 201110360282.2 and 201110360267.8) formerly.These several hard carbon material capacity have reached more than the 500mAh/g, and high rate performance and cryogenic property all are better than the conventional graphite negative pole.But, because the defective of hard carbon material own is more, so although through modification, generally its irreversible capacity all is higher than 10%.And the charge and discharge platform of hard carbon material own is very near lithium metal, lithium easily occurs in charging process separate out, and then make the battery danger that is short-circuited.These have hindered hard carbon material large-scale commercial applications use on lithium ion battery.
Lithium titanate (chemical formula Li4Ti5O12) is a kind of lithium cell cathode material newly developed in recent years.Lithium titanate is 1.55V with respect to the current potential of lithium electrode, and far above graphite and hard carbon material, so the first efficient of lithium titanate anode is higher than 95%, and lithium metal can not occur in charge and discharge process yet separates out, and can improve the security performance of battery.In addition, embed or deviate from the process at Li, crystal formation does not change, therefore change in volume is called as " zero strain material " less than 1%, and this is significant, can avoid in the charge and discharge cycles owing to stretching back and forth of electrode material causes structural damage, thereby improve cycle performance and the useful life of electrode, reduced with the cycle-index increase and brought specific capacity significantly to decay, make lithium titanate have better cycle performance.But the lithium titanate theoretical specific capacity is 175mAh/g, and actual specific capacity 150～160mAh/g far below carbon class negative material, can not satisfy the demand of lithium battery high-energy-density.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 soon high-power winding column type lithium ion battery ", this disclosure of the invention a kind of high-power winding column type lithium ion battery that fills soon, comprise anode pole piece, cathode pole piece, porous isolating membrane, reel successively and become the pillar core body, and at core extracorporeal set metal shell, electrolyte is annotated in metal shell, it is characterized in that: positive electrode is cobalt acid lithium, LiMn2O4, the element material, nickel cobalt lithium aluminate, LiFePO 4, wherein one or more of lithium vanadate; Negative material is one or more in graphite, the lithium titanate.Plus plate current-collecting body is thickness at 8～30 microns preliminary treatment aluminium foil or aluminium net; Negative current collector is thickness at 8～30 microns Copper Foil, copper mesh, iron nickel plating paper tinsel or iron nickel plating net.Electrolyte in the electrolyte is that a kind of of lithium hexafluoro phosphate, biethyl diacid lithium borate or two kinds mix; Solvent in the electrolyte is two kinds or several mixing of EC, PC, DMC, DEC, EA etc.The present invention can realize that the battery high-power output also can realize filling soon of battery, and security performance is high.
Negative pole uses one or more of graphite, lithium titanate in the above-mentioned patent, and from aforementioned discussion as can be known, 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 is just mixed use with graphite and lithium titanate, and at micro-scale the two is not carried out compound, therefore fail to take full advantage of the lithium titanate height first the advantage shortcoming that graphite electrolyte poor compatibility and cyclicity is poor of efficient and excellent cycle cover.
Summary of the invention
The present invention is intended to solve in the above-mentioned prior art hard carbon material, and efficient is low first, easily analyse lithium, the lithium titanate material capacity is low, and the problem that conductivity is low provides a kind of lithium battery tertiary negative material, it is large that this material has specific capacity, efficient is high first, and high rate performance and cryogenic property are good, and irreversible capacity is low, the advantage that fail safe and cycle life are good has been agreed with the right demand of new type lithium ion battery.
Another object of the present invention provides a kind of preparation method of above-mentioned lithium battery tertiary negative material, its objective is to use simple technique and cheap cost to obtain high performance tri compound negative material.
In order to realize the foregoing invention purpose, 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 titanyl compound, titanium salt or the titanium simple substance as the titanium source, as the lithium salts in lithium source, make as the starch of hard carbon precursor and expanded graphite, comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
50～98 parts of hard charcoals
1.5～45 parts of lithium titanates
0.5～5.0 part of expanded graphite.
Titanyl compound of the present invention, titanium salt or titanium simple substance are the conventional articles for use in this area, 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 lithium hydroxide, lithium oxalate, lithium acetate, lithium carbonate, lithia, lithium sulfate, lithium nitrate, lithium chloride of this area routine etc.
The preferred lithium carbonate of above-mentioned lithium salts.
Lithium battery tertiary composite negative pole material in the 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, below preferably provide a kind of preparation technology simpler and with low cost:
A kind of preparation method of lithium battery tertiary composite negative pole material is characterized in that: comprise following processing step:
A, take by weighing lithium source and titanium source by elemental lithium and titanium elements atomic ratio 3:5～5:5, then take by weighing starch according to starch and titanium source quality than 10:1～100:1, three kinds of raw materials are evenly mixed, obtain the mixed-powder of lithium source, titanium source and starch;
B, take by weighing deionized water, ethanol or acetone as dispersant with liquid quality than for 1:10～1:100 according to the mixed-powder of the lithium source that obtains in the steps A, titanium source and starch, the mixed-powder of the lithium source, titanium source and the starch that obtain in dispersant and the steps A is mixed, obtain mixed slurry;
C, mixed slurry was stirred 1～10 hour, with the dispersant oven dry, obtain drying powder;
D, get the oven dry powder put into heating furnace, the heating rate with 0.1～1 ℃/min under inert atmosphere rises to 600～1000 ℃, then heat treated 0.2～5h is cooled to room temperature under inert atmosphere, obtain cooling off powder;
E, will cool off powder and expanded graphite in mass ratio the ratio of 10:1～100:1 mix, join in the solvent of 10～20 times of volumes, stir or ultrasonic concussion 0.5～5h, then use the mode of centrifugal, filtration or suction filtration with 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 steps A, described lithium source and the titanium source of taking by weighing is for being that 4:5 takes by weighing according to elemental lithium and titanium elements atomic ratio.
In steps A, described titanium source particle diameter is 10～1000nm of this area routine, and preferable particle size is 50nm.
In steps A, described starch is the cereal starch (such as rice starch, cornstarch, sorghum starch, wheaten starch etc.) of this area routine, potato starch (such as tapioca, sweet potato starch, farina etc.), a kind of among bean starch (such as green starch, Faba bean starch, pea starch etc.) and/or other kind of starch (such as Tapioca starch, lotus root starch, Chinese Water Chestnut Starch, acorn starch), or several arbitrary proportion mixtures.
In step B, the mixed-powder of described lithium source, titanium source and starch is 1:20 with the liquid quality ratio.
In step C, described mixed slurry is stirred referred to enter high-energy ball milling, ball milling 1～10 hour in 1～10 hour.
Above-mentioned high-energy ball milling is conventional planetary ball mill or sand mill, and rotating speed is 300～1000r/min, preferred 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, conventional products or directly purchase that described expanded graphite makes for adopting techniques well known.
In step e, described solvent is conventional water, ethanol, acetone, toluene, n-hexane, cyclohexane, benzene or dimethylbenzene, preferred alcohol.
Refer to that in the stirring described in the step e 100～1500r/min stirs 1～4h with rotating speed under 20～80 ℃ of temperature.
According to the problem of mentioning in the background technology, and the situation of prior art development, for these reasons, the present invention has developed the hard charcoal/lithium titanate of a kind of sphere/expanded graphite tri compound negative material, this material has had both height ratio capacity and the high magnification characteristic of hard charcoal, the height of lithium titanate is efficient, fail safe and cycle life first, and the good electric conductivity of graphite.Therefore, it is large that this composite negative pole material has specific capacity, and efficient is high first, and high rate performance and cryogenic property are good, and irreversible capacity is low, and the advantage that fail safe and cycle life are good has been agreed with the right demand of new type lithium ion battery.
Among the present invention, we use capacity higher (can be higher than 400mAh/g), and the electrolyte compatibility is good, and charcoal is as the material kernel firmly for the good sphere of high rate performance, and the use lithium titanate coats hard charcoal, and lithium titanate directly contacts with electrolyte like this.In order further to improve material electric conductivity and multiplying power property, again that the expanded graphite of the hard charcoal/lithium titanate of sphere and excellent electric conductivity is compound, with expanded graphite as the space conductive network.The sphere that obtains like this is charcoal/lithium titanate/expanded graphite tri compound negative material firmly, has had both height ratio capacity and the high magnification characteristic of hard charcoal, and the height of lithium titanate is efficient, fail safe and cycle life first, and the good electric conductivity of graphite.Therefore, it is large that this composite negative pole material has specific capacity, and efficient is high first, and high rate performance and cryogenic property are good, and irreversible capacity is low, and the advantage that fail safe and cycle life are good has been agreed with the right demand of new type lithium ion battery.
The present invention has brought following useful technique effect:
1, the cost of material used of this method is cheap, and the source is abundant, is easy to realize large-scale industrial production; The present invention utilizes the intrinsic pattern of starch material, need not through special balling technique, and spherical compound, technique and equipment are simple, and energy consumption is low; Therefore the composite material of the present invention's preparation possesses height ratio capacity and high magnification characteristic and the good cryogenic property of hard charcoal take hard charcoal as main body; The composite material of the present invention preparation is coated on lithium titanate the skin of hard charcoal, and the height that therefore has a lithium titanate is efficient, fail safe and cycle life first; The composite material of the present invention's preparation has the three-dimensional conductive network that expanded graphite forms, utilize the conduction of building as electronics of solid spacial framework that good passage is provided, thereby improve the voltage delay effect of hard carbon material, also overcome the defective of the low electronic conductivity of lithium titanate material; It is large that composite negative pole material disclosed by the invention has specific capacity, and efficient is high first, and high rate performance and cryogenic property are good, and irreversible capacity is low, and the advantage that fail safe and cycle life are good has been agreed with the right demand of new type lithium ion battery.
2, the preferred lithium carbonate in lithium source in the ternary anode material of the present invention is so that cheap, when reducing old, can react the lithium titanate that obtains function admirable.
3, preparation method of the present invention in steps A, is that 4:5 takes by weighing lithium source and titanium source according to elemental lithium and titanium elements atomic ratio preferably, is beneficial to obtain pure lithium titanate, improves the quality of final product; It also is nanoscale that nano level titanium source makes the lithium titanate particle diameter that obtains, and the lithium ion migration path is short, is beneficial to the raising battery performance, and preferred 50nm is an only particle diameter, also is easy to directly buy obtain, and reduces old, has improved production efficiency.
4, preparation method of the present invention, in step B, the mixed-powder of described lithium source, titanium source and starch compares preferably 1:20 with liquid quality, the composite material charcoal that obtains like this accounts for greatly about 80%, lithium titanate accounts for about 15%, the hard charcoal proportion that had both guaranteed high power capacity is high, guarantees that again covered effect is good, so that material property is good.
5, preparation method of the present invention, in step C, the preferred high-energy ball milling of described stirring is so that it is more even to mix dispersion; In addition, rotating speed is excessively low to be unfavorable for mixing fully, and rotating speed is too high high to equipment and energy consumption requirement, and may destroy sphericity, and preferred rotating speed is 800 r/min, can guarantee that material fully contacts mixing, guarantees 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, makes the material consistency better; Inert gas preferred nitrogen in step D, the solvent preferred alcohol can guarantee economy in step e, reduces production costs, and can guarantee the quality of final product simultaneously.
Description of drawings
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 titanyl compound, titanium salt or the titanium simple substance as the titanium source, as the lithium salts in lithium source, make as the starch of hard carbon precursor and expanded graphite, comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
50 parts of hard charcoals
1.5 parts of lithium titanates
0.5 part of expanded graphite.
Preferably: 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 titanyl compound, titanium salt or the titanium simple substance as the titanium source, as the lithium salts in lithium source, make as the starch of hard carbon precursor and expanded graphite, comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
98 parts of hard charcoals
45 parts of lithium titanates
5 parts of expanded graphites.
Preferably: 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 titanyl compound, titanium salt or the titanium simple substance as the titanium source, as the lithium salts in lithium source, make as the starch of hard carbon precursor and expanded graphite, comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
74 parts of hard charcoals
23.25 parts of lithium titanates
2.75 parts of expanded graphites.
Preferably: 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 titanyl compound, titanium salt or the titanium simple substance as the titanium source, as the lithium salts in lithium source, make as the starch of hard carbon precursor and expanded graphite, comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
60 parts of hard charcoals
41 parts of lithium titanates
1.2 parts of expanded graphites.
Preferably: described lithium salts is lithium carbonate.
Embodiment 5
A kind of preparation method of lithium battery tertiary composite negative pole material comprises following processing step:
A, take by weighing lithium source and titanium source by elemental lithium and titanium elements atomic ratio 3:5, then take by weighing starch according to starch and titanium source quality than 10:1, three kinds of raw materials are evenly mixed, obtain the mixed-powder of lithium source, titanium source and starch;
B, according to the mixed-powder of the lithium source that obtains in the steps A, titanium source and starch and liquid quality than taking by weighing deionized water, ethanol or acetone as dispersant for 1:10, the mixed-powder of the lithium source, titanium source and the starch that obtain in dispersant and the steps A is mixed, obtain mixed slurry;
C, mixed slurry was stirred 1 hour, with the dispersant oven dry, obtain drying powder;
D, get the oven dry powder put into heating furnace, the heating rate with 0.1 ℃/min under inert atmosphere rises to 600 ℃, then heat treated 0.2h is cooled to room temperature under inert atmosphere, obtain cooling off powder;
E, will cool off powder and expanded graphite in mass ratio the ratio of 10:1 mix, join in the solvent of 10 times of volumes, stir or ultrasonic concussion 0.5h, then use the mode of centrifugal, filtration or suction filtration with 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 kind of preparation method of lithium battery tertiary composite negative pole material comprises following processing step:
A, take by weighing lithium source and titanium source by elemental lithium and titanium elements atomic ratio 5:5, then take by weighing starch according to starch and titanium source quality than 100:1, three kinds of raw materials are evenly mixed, obtain the mixed-powder of lithium source, titanium source and starch;
B, according to the mixed-powder of the lithium source that obtains in the steps A, titanium source and starch and liquid quality than taking by weighing deionized water, ethanol or acetone as dispersant for 1:100, the mixed-powder of the lithium source, titanium source and the starch that obtain in dispersant and the steps A is mixed, obtain mixed slurry;
C, mixed slurry was stirred 10 hours, with the dispersant oven dry, obtain drying powder;
D, get the oven dry powder put into heating furnace, the heating rate with 1 ℃/min under inert atmosphere rises to 1000 ℃, then heat treated 5h is cooled to room temperature under inert atmosphere, obtain cooling off powder;
E, will cool off powder and expanded graphite in mass ratio the ratio of 100:1 mix, join in the solvent of 20 times of volumes, stir or ultrasonic concussion 5h, then use the mode of centrifugal, filtration or suction filtration with 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 kind of preparation method of lithium battery tertiary composite negative pole material comprises following processing step:
A, take by weighing lithium source and titanium source by elemental lithium and titanium elements atomic ratio 4:5, then take by weighing starch according to starch and titanium source quality than 55:1, three kinds of raw materials are evenly mixed, obtain the mixed-powder of lithium source, titanium source and starch;
B, according to the mixed-powder of the lithium source that obtains in the steps A, titanium source and starch and liquid quality than taking by weighing deionized water, ethanol or acetone as dispersant for 1:55, the mixed-powder of the lithium source, titanium source and the starch that obtain in dispersant and the steps A is mixed, obtain mixed slurry;
C, mixed slurry was stirred 5.5 hours, with the dispersant oven dry, obtain drying powder;
D, get the oven dry powder put into heating furnace, the heating rate with 0.55 ℃/min under inert atmosphere rises to 800 ℃, then heat treated 2.6h is cooled to room temperature under inert atmosphere, obtain cooling off powder;
E, will cool off powder and expanded graphite in mass ratio the ratio of 55:1 mix, join in the solvent of 15 times of volumes, stir or ultrasonic concussion 2.75h, then use the mode of centrifugal, filtration or suction filtration with 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 kind of preparation method of lithium battery tertiary composite negative pole material comprises following processing step:
A, take by weighing lithium source and titanium source by elemental lithium and titanium elements atomic ratio 3.6:5, then take by weighing starch according to starch and titanium source quality than 88:1, three kinds of raw materials are evenly mixed, obtain the mixed-powder of lithium source, titanium source and starch;
B, according to the mixed-powder of the lithium source that obtains in the steps A, titanium source and starch and liquid quality than taking by weighing deionized water, ethanol or acetone as dispersant for 1:21, the mixed-powder of the lithium source, titanium source and the starch that obtain in dispersant and the steps A is mixed, obtain mixed slurry;
C, mixed slurry was stirred 3 hours, with the dispersant oven dry, obtain drying powder;
D, get the oven dry powder put into heating furnace, the heating rate with 0.27 ℃/min under inert atmosphere rises to 950 ℃, then heat treated 0.9h is cooled to room temperature under inert atmosphere, obtain cooling off powder;
E, will cool off powder and expanded graphite in mass ratio the ratio of 36:1 mix, join in the solvent of 18 times of volumes, stir or ultrasonic concussion 3.5h, then use the mode of centrifugal, filtration or suction filtration with 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 steps A, described lithium source and the titanium source of taking by weighing is for being that 4:5 takes by weighing according to elemental lithium and titanium elements atomic ratio.
In steps A, described titanium source particle diameter is 50nm.
In step B, the mixed-powder of described lithium source, titanium source and starch is 1:20 with the liquid quality ratio.
In step C, described mixed slurry is stirred referred to enter high-energy ball milling, ball milling 1 hour in 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 to that in the stirring described in the step e 100r/min stirs 1h with rotating speed under 20 ℃ of temperature.
Embodiment 10
On the basis of embodiment 5～8, preferably:
In steps A, described lithium source and the titanium source of taking by weighing is for being that 4:5 takes by weighing according to elemental lithium and titanium elements atomic ratio.
In steps A, described titanium source particle diameter is 50nm.
In step B, the mixed-powder of described lithium source, titanium source and starch is 1:20 with the liquid quality ratio.
In step C, described mixed slurry is stirred referred to enter high-energy ball milling, ball milling 10 hours in 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 to that in the stirring described in the step e 1500r/min stirs 4h with rotating speed under 80 ℃ of temperature.
Embodiment 11
On the basis of embodiment 5～8, preferably:
In steps A, described lithium source and the titanium source of taking by weighing is for being that 4:5 takes by weighing according to elemental lithium and titanium elements atomic ratio.
In steps A, described titanium source particle diameter is 50nm.
In step B, the mixed-powder of described lithium source, titanium source and starch is 1:20 with the liquid quality ratio.
In step C, described mixed slurry is stirred referred to enter high-energy ball milling, ball milling 5.5 hours in 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 to that in the stirring described in the step e 800r/min stirs 2.5h with rotating speed under 50 ℃ of temperature.
Embodiment 12
On the basis of embodiment 5～8, preferably:
In steps A, described lithium source and the titanium source of taking by weighing is for being that 4:5 takes by weighing according to elemental lithium and titanium elements atomic ratio.
In steps A, described titanium source particle diameter is 50nm.
In step B, the mixed-powder of described lithium source, titanium source and starch is 1:20 with the liquid quality ratio.
In step C, described mixed slurry is stirred referred to enter high-energy ball milling, ball milling 3 hours in 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 to that in the stirring described in the step e 500r/min stirs 2h with rotating speed under 66 ℃ of temperature.
Embodiment 13
The hard charcoal capacity 480mAh/g that the present invention uses, lithium titanate capacity 160mAh/g, compound in ratio of the present invention after, capacity is 350-470 mAh/g, far above the lithium titanate capacity, also is higher than the capacity of graphite cathode.The negative material that the present invention obtains first efficient is 88-94%, far above about 70% of hard carbon material.After tested, negative material of the present invention can be fully compatible in PC base low-temperature electrolyte, and capability retention is higher than 90% after 3000 circulations, and does not analyse the 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 the 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; With slurry dual coating on 16 microns aluminium foil; Under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2
Cathode composition and negative pole: adopting the composite material of the embodiment 1～4 that preparation negative material technique prepares among the embodiment 5～8 is negative electrode active material, and the method in common knowledge according to those skilled in the art prepares cathode size; With cathode size dual coating on 12 microns Copper Foil, under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-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: with positive pole and the negative pole of said method preparation, 20 microns PE perforated membrane is barrier film, and the order lamination with negative pole/barrier film/positive pole/barrier film/negative pole in humidity-controlled environment makes.
Comparative Examples 1: adopt said method to prepare lithium ion battery, the difference negative material is conventional 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 the 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; With slurry dual coating on 16 microns aluminium foil; Under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2
Cathode composition and negative pole: adopting the composite material of the embodiment 1～4 that preparation negative material technique prepares among the embodiment 5～8 is negative electrode active material, and the method in common knowledge according to those skilled in the art prepares cathode size; With cathode size dual coating on 12 microns Copper Foil, under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-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: with positive pole and the negative pole of said method preparation, 20 microns PE perforated membrane is barrier film, and the order lamination with negative pole/barrier film/positive pole/barrier film/negative pole in humidity-controlled environment makes.
Comparative Examples 2: adopt said method to prepare lithium ion battery, the difference negative material is conventional 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 the 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; With slurry dual coating on 16 microns aluminium foil; Under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2
Cathode composition and negative pole: adopting the composite material of the embodiment 1～4 that preparation negative material technique prepares among the embodiment 5～8 is negative electrode active material, and the method in common knowledge according to those skilled in the art prepares cathode size; With cathode size dual coating on 12 microns Copper Foil, under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-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: with positive pole and the negative pole of said method preparation, 20 microns PE perforated membrane is barrier film, and the order lamination with negative pole/barrier film/positive pole/barrier film/negative pole in humidity-controlled environment makes.
Comparative Examples 3: adopt said method to prepare lithium ion battery, the difference negative material is conventional 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 the 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; With slurry dual coating on 16 microns aluminium foil; Under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2
Cathode composition and negative pole: adopting the composite material of the embodiment 1～4 that preparation negative material technique prepares among the embodiment 5～8 is negative electrode active material, and the method in common knowledge according to those skilled in the art prepares cathode size; With cathode size dual coating on 12 microns Copper Foil, under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-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: with positive pole and the negative pole of said method preparation, 20 microns PE perforated membrane is barrier film, and the order lamination with negative pole/barrier film/positive pole/barrier film/negative pole in humidity-controlled environment makes.
Comparative Examples 4: adopt said method to prepare lithium ion battery, the difference negative material is conventional 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 the 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; With slurry dual coating on 16 microns aluminium foil; Under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2
Cathode composition and negative pole: adopting the composite material of the embodiment 1～4 that preparation negative material technique prepares among the embodiment 5～8 is negative electrode active material, and the method in common knowledge according to those skilled in the art prepares cathode size; With cathode size dual coating on 12 microns Copper Foil, under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-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: with positive pole and the negative pole of said method preparation, 20 microns PE perforated membrane is barrier film, and the order lamination with negative pole/barrier film/positive pole/barrier film/negative pole in humidity-controlled environment makes.
Comparative Examples 5: adopt said method to prepare lithium ion battery, the difference negative material is conventional 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 the 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; With slurry dual coating on 16 microns aluminium foil; Under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2
Cathode composition and negative pole: adopting the composite material of the embodiment 1～4 that preparation negative material technique prepares among the embodiment 5～8 is negative electrode active material, and the method in common knowledge according to those skilled in the art prepares cathode size; With cathode size dual coating on 12 microns Copper Foil, under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-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: with positive pole and the negative pole of said method preparation, 20 microns PE perforated membrane is barrier film, and the order lamination with negative pole/barrier film/positive pole/barrier film/negative pole in humidity-controlled environment makes.
Comparative Examples 6: adopt said method to prepare lithium ion battery, the difference negative material is conventional 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 the 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; With slurry dual coating on 16 microns aluminium foil; Under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.0mAh/cm
2
Cathode composition and negative pole: adopting the composite material of the embodiment 1～4 that preparation negative material technique prepares among the embodiment 5～8 is negative electrode active material, and the method in common knowledge according to those skilled in the art prepares cathode size; With cathode size dual coating on 12 microns Copper Foil, under 90 ℃ of conditions vacuum bakeout 3.5h(vacuum degree for-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: with positive pole and the negative pole of said method preparation, 20 microns PE perforated membrane is barrier film, and the order lamination with negative pole/barrier film/positive pole/barrier film/negative pole in humidity-controlled environment makes.
Comparative Examples 7: adopt said method to prepare lithium ion battery, the difference negative material is conventional graphite.
Embodiment 21
Electrochemical property test
Embodiment 14～20 and Comparative Examples 1～7 prepared battery capacity are 450mAh(1C).Under the room temperature, the lithium ion battery that embodiment 14～20 and Comparative Examples 1～7 are made is take the initial charge current density as 0.2mAh/cm
2The lithium ion battery upper voltage limit 4.2V that makes of embodiment 14～17 and Comparative Examples 1～4 wherein, lower voltage limit 3.0V; The lithium ion battery upper voltage limit 3.8V that embodiment 18～20 and Comparative Examples 5～7 make, lower voltage limit 2.5V.
With the capacity of battery test battery under the large multiplying power of normal temperature 1C, 10C, 0 ℃ of low temperature discharge, 1000 conditions of normal temperature 1C circulation, and the calculated capacity surplus ratio, as shown in table 1.
Table 1
Can find out 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 good, the electrolyte compatibility is good, stable cycle performance it seems that comprehensively various aspects of performance all is far superior to the lithium battery of existing graphite cathode preparation.
Claims (10)
1. lithium battery tertiary composite negative pole material, it is characterized in that: described lithium battery tertiary composite negative pole material is: by titanyl compound, titanium salt or the titanium simple substance as the titanium source, as the lithium salts in lithium source, make as the starch of hard carbon precursor and expanded graphite, comprise the lithium battery tertiary composite negative pole material of following parts by weight component:
50～98 parts of hard charcoals
1.5～45 parts of lithium titanates
0.5～5 part of expanded graphite.
2. a kind of lithium battery tertiary composite negative pole material according to claim 1, it is characterized in that: described lithium salts is lithium carbonate.
3. the preparation method of a kind of lithium battery tertiary composite negative pole material according to claim 1 is characterized in that: comprise following processing step:
A, take by weighing lithium source and titanium source by elemental lithium and titanium elements atomic ratio 3:5～5:5, then take by weighing starch according to starch and titanium source quality than 10:1～100:1, three kinds of raw materials are evenly mixed, obtain the mixed-powder of lithium source, titanium source and starch;
B, take by weighing deionized water, ethanol or acetone as dispersant with liquid quality than for 1:10～1:100 according to the mixed-powder of the lithium source that obtains in the steps A, titanium source and starch, the mixed-powder of the lithium source, titanium source and the starch that obtain in dispersant and the steps A is mixed, obtain mixed slurry;
C, mixed slurry was stirred 1～10 hour, with the dispersant oven dry, obtain drying powder;
D, get the oven dry powder put into heating furnace, the heating rate with 0.1～1 ℃/min under inert atmosphere rises to 600～1000 ℃, then heat treated 0.2～5h is cooled to room temperature under inert atmosphere, obtain cooling off powder;
E, will cool off powder and expanded graphite in mass ratio the ratio of 10:1～100:1 mix, join in the solvent of 10～20 times of volumes, stir or ultrasonic concussion 0.5～5h, then use the mode of centrifugal, filtration or suction filtration with solid and separated from solvent, then in drying box, solvent is dried, namely obtain hard charcoal/lithium titanate/expanded graphite tri compound negative material.
4. the preparation method of a kind of lithium battery tertiary composite negative pole material according to claim 3 is characterized in that: in steps A, described lithium source and the titanium source of taking by weighing is for being that 4:5 takes by weighing according to elemental lithium and titanium elements atomic ratio.
5. the preparation method of a kind of lithium battery tertiary composite negative pole material according to claim 3, it is characterized in that: in steps A, described titanium source particle diameter is 50nm.
6. the preparation method of a kind of lithium battery tertiary composite negative pole material according to claim 3 is characterized in that: in step B, the mixed-powder of described lithium source, titanium source and starch and liquid quality are than being 1:20.
7. the preparation method of a kind of lithium battery tertiary composite negative pole material according to claim 3 is characterized in that: in step C, described mixed slurry is stirred referred to enter high-energy ball milling, ball milling 1～10 hour in 1～10 hour.
8. the preparation method of a kind of lithium battery tertiary composite negative pole material according to claim 7, it is characterized in that: described high-energy ball milling rotating speed is 800 r/min.
9. the preparation method of a kind of lithium battery tertiary composite negative pole material according to claim 3, it is characterized in that: in step D, described heating furnace is rotary furnace.
10. the preparation method of a kind of lithium battery tertiary composite negative pole material according to claim 3 is characterized in that: refer to that in the stirring described in the step e 100～1500r/min stirs 1～4h with rotating speed under 20～80 ℃ of temperature.
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| 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 |
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