CN102623698A - Titanium lithium silicate, preparation method thereof and use of the same serving as electrode material of lithium battery - Google Patents
Titanium lithium silicate, preparation method thereof and use of the same serving as electrode material of lithium battery Download PDFInfo
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- CN102623698A CN102623698A CN2012101114142A CN201210111414A CN102623698A CN 102623698 A CN102623698 A CN 102623698A CN 2012101114142 A CN2012101114142 A CN 2012101114142A CN 201210111414 A CN201210111414 A CN 201210111414A CN 102623698 A CN102623698 A CN 102623698A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 45
- 229910052912 lithium silicate Inorganic materials 0.000 title claims abstract description 31
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000007772 electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 42
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims description 38
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 25
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 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 claims description 2
- 239000010406 cathode material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 21
- 239000007773 negative electrode material Substances 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 41
- 239000003792 electrolyte Substances 0.000 description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- 239000012153 distilled water Substances 0.000 description 30
- 238000001035 drying Methods 0.000 description 29
- 239000003921 oil Substances 0.000 description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 24
- 239000011734 sodium Substances 0.000 description 24
- 239000010936 titanium Substances 0.000 description 22
- 210000004027 cell Anatomy 0.000 description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229910002804 graphite Inorganic materials 0.000 description 17
- 239000010439 graphite Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 15
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 15
- 229910013870 LiPF 6 Inorganic materials 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 description 15
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 15
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 15
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 15
- 238000001914 filtration Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- 239000012528 membrane Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 238000000634 powder X-ray diffraction Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 101100065719 Drosophila melanogaster Ets98B gene Proteins 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 229910008484 TiSi Inorganic materials 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- -1 silicon lithium titanate salt Chemical class 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical class Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- OEMQKIFQLKSVBJ-UHFFFAOYSA-N [Si]([O-])([O-])([O-])[O-].[Ti+4].[Li+] Chemical class [Si]([O-])([O-])([O-])[O-].[Ti+4].[Li+] OEMQKIFQLKSVBJ-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-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
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940125717 barbiturate Drugs 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical class [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides titanium lithium silicate serving as an electrode material of a lithium battery. The titanium lithium silicate serving as the electrode material of the lithium battery is manufactured through the exchange of a metal titanium silicate precursor with a two-dimensional layered structure or a three-dimensional framework structure with lithium ions. The titanium lithium silicate can be used for preparing a negative electrode material of the lithium ion battery. The titanium lithium silicate material provided by the invention has a low discharge plateau, high electric capacitance, good cyclic charge-discharge performance, and the like when serving as the negative electrode material of the lithium ion battery. The invention provides a preparation method of the titanium lithium silicate electrode material, and the titanium lithium silicate electrode material provided by the invention is simple to easy to prepare, has high repeatability and is a superior electrode material. The invention discloses the preparation method of the titanium lithium silicate.
Description
Technical field:
The invention belongs to the electrode material of lithium battery field, be specifically related to a kind of new titanium-silicone Barbiturates electrode material of lithium battery.
Technical background:
Lithium ion battery is a kind of rechargeable battery, and it mainly relies on lithium ion in charge and discharge process, between positive pole and negative pole, to move work, accomplishes the charging and the discharge of battery through the process of embedding lithium-Tuo lithium.Lithium ion battery has been widely used in various portable type electronic products and the communication tool as a kind of high performance secondary green battery, because its superior performance, lithium ion battery also becomes potential electrokinetic cell, and its research receives people's attention always.
The electrode of lithium ion battery is general to adopt the material that contains elemental lithium [referring to J.-M.Tarascon, M.Armand, Issues and challenges facing rechargeable lithium batteries; [J] Nature; 2001,414,359-367.].Existing anode material for lithium-ion batteries comprises the embedding lithium transition-metal oxide of stratiform, like LiMO
2(M=Co, Ni, Mn, V etc.), the LiM of three-dimensional spinel structure
2O
4(M=Mn, Co, V etc. and based on XO
mThe matrix type polyanionic compound that (X=P, Si, S, B, V, W, Mo etc., m=3,4,5,6) unit is constructed.Existing lithium ion battery negative material roughly is divided into following several types: the one, traditional be applied to business-like carbon negative pole material; The 2nd, the alloy type negative material is like tinbase, silica-based, aluminium base etc.; The 3rd, nano-metal-oxide is like Fe
2O
3, CuO, TiO
2Deng; The 4th, the composite oxides slaine is like lithium titanate etc.
Material with carbon element is most widely used now lithium ion battery negative material, and it has good stability, and the theoretical capacitance of graphite mould carbon is 372mAh/g, and the capacitance of the material with carbon element of practical application is about 200mAh/g.Material with carbon element has advantages such as easy preparation as lithium ion battery negative, and problems such as energy loss that still existence is bigger and high-rate charge-discharge capability difference [referring to: W.Kohs, H.J.Santner, F.Hofer; H.Schrottner, J.Doninger, I.Barsukov, H.Buqa; JH.Albering, K.-C.Moiler, J.O.Besenhard, M.Winter; A study on electrolyte interactions with graphite anodes exhibiting structures with various amounts of rhombohedral phase, [J] Journal of Power Sources, 2003; 119-121,528-537.], material with carbon element very easily forms passivating film in organic bath; Cause the irreversible loss of specific capacity, and carbon electrode current potential and lithium current potential are very approaching, cause Zhi Jing to cause that short circuit is [referring to J.-M.Tarascon easily; M.Armand, Issues and challenges facing rechargeable lithium batteries, [J] Nature; 2001,414,359-367.].Alloy type negative material such as tinbase, silica-base material have very high specific capacity, and density is moderate, and electrode potential is high slightly than lithium; Can avoid the generation of dendrite, but this type material cyclical stability is relatively poor, change in volume is very big in the charge and discharge process; It is very fast [referring to C.-M.Park, J.-H.Kim, H.Kim that final efflorescence causes capacity to descend; H.-J.Sohn, Li-alloy based anode materials for Li secondary batteries, [J] Chem.Soc.Rev.; 2010,39,3115-3141].Nano-metal-oxide possibly react with electrolyte in discharging and recharging as negative material, and reunite easily, causes cycle performance of battery poor [referring to A.S.Aric ò; P.Bruce, B.Scrosati, J.-M.Tarascon; W.van Schalkwijk, Nanostructured materials for advanced energy conversion and storage devices, [J] Nature Materials; 2005,4,366-377.].Composite metal oxide such as lithium titanate crystal structure are stable, and the charge and discharge process change in volume is little, as GND extraordinary cyclical stability is arranged, and discharge platform is stable; But the discharge platform of not enough is titanate causes working voltage platform low up to 1.55V, and capacitance is little; And electrolyte is required harsh, its preparation is than difficulty etc. in addition, causes its application to receive limitation [referring to B.Scrosati; J.Garche, Lithium batteries:Status, prospects and future; [J] Journal of Power Sources 2010,195,2419-2430.].
Silicotitanate is reported seldom as the research of lithium ion battery electrode material.Patoux and Masquelier have studied has α-VPO
5The Li of structure
2TiSiO
5As the performance of lithium ion cell electrode, they find that this material does not have that lithium ion inserts and embedded performance, are not suitable for as lithium ion cell electrode [referring to S.Patoux; C.Masquelier, Lithium insertion into titanium phosphates, silicates; And sulfates; [J] Chem.Mater.2002,14,5057-5068.].People such as N.A.Milne have studied three-dimensional structure micropore titanium silicon hydrochlorate sitinakite and (have consisted of Na
2Ti
2O
3SiO
42.76H
2O) lithium ion inserts and embedded performance, finds that this material can be used as the negative pole of lithium ion battery, and after 20 charging and discharging circulations, its capacitance reaches 180-200mAh g
-1, but cycle performance is than lithium titanate difference, and voltage platform is littler [referring to N.A.Milne; C.S.Griffith, J.V.Hanna, M.Skyllas-Kazacos; V.Luca, Lithium intercalation into the titanosilicate sitinakite, [J] Chem.Mater.2006; 18,3192-3202.].People such as Kuznicki have synthesized a new titanium-silicone hydrochlorate ETS-14 in its patent, have the lithium ion switching performance, claim the positive electrode that can be used as lithium ion battery; But there are not concrete performance data [S.M.Kuznicki, J.S.Curran, X.Yang; ETS-14crystalline titanium silicate molecular sieves; Manufacture and use thereof, [P] US Patent 5882624,1999.]
The research of lithium ion battery negative material has great significance to improving the lithium ion battery combination property, and the new material developmental research has wide development space, is one of lithium ion battery Research on development emphasis.
Summary of the invention
The purpose of this invention is to provide a kind of Novel Titanium silicic acid lithium salts class electrode material, for the application of lithium ion battery provides selection of electrode materials with good lithium ion battery characteristic.
Technical scheme of the present invention is following:
A kind of titanium lithium metasilicate as electrode material of lithium battery, it is a Titanium silicate predecessor with two-dimensional layer or three-dimensional framework structure through making the titanium lithium metasilicate of electrode material of lithium battery with lithium ion ion-exchange.
The above-mentioned titanium lithium metasilicate as electrode material of lithium battery, described Titanium silicate predecessor with two-dimensional layer or three-dimensional framework structure is that JDF-L1 (claims AM-1 again, Na
4Ti
2Si
8O
224H
2O), fresnoite (Ba
2TiSi
2O
8), AM-4 (Na
3(Na, H) Ti
2Si
4O
142H
2O), natisite (Na
2TiOSiO
4), Zorite (claims ETS-4 again, Na
6Ti
5Si
12O
35(OH)
411H
2O), ETS-10 (M
2TiSi
5O
134H
2O, M are Na or K), JLU-1, pharmacosiderite (HM
3Ti
4Si
3O
164H
2O, M=H, K, Cs), GTS-1 (Na
2Ti
2O
3SiO
42H
2O), AM-2 (claims umbite again, K
2Ti
xZr
1-xSi
3O
9H
2O, 0≤x≤1), UND-1 (Na
2.7K
5.3Ti
4Si
12O
364H
2O), penkvilksite (claims penkvilksite-1M again, penkvilksite-2O, or AM-3, Na
4Ti
2Si
8O
225H
2O), nenadkevichite (ANbTi
xSi
2O
7H
2O, 0.8≤x≤17.1, A=Na, Ca) or vinagradovite (Na
8Ti
8Si
16O
52), have chemical formula: A
wM
xTi
ySiO
zNH
2O, wherein: A be alkali metal or alkaline-earth metal or hydrogen with and composition thereof, M is a transition metal, 0≤w≤10,0≤x≤5,0＜y≤5,0＜z≤10,0≤n≤20 are natural or the Titanium silicate of synthetic preparation.
A kind of method for preparing above-mentioned titanium lithium metasilicate, it is that Titanium silicate is mixed with the solubility Aqueous Lithium Salts, at 100 ℃ of stirring reaction 24-100 hours, promptly gets white powder, as the titanium lithium metasilicate of electrode material of lithium battery.
The preparation method of above-mentioned titanium lithium metasilicate, described Titanium silicate predecessor with two-dimensional layer or three-dimensional framework structure is that JDF-L1 (claims AM-1 again, Na
4Ti
2Si
8O
224H
2O), fresnoite (Ba
2TiSi
2O
8), AM-4 (Na
3(Na, H) Ti
2Si
4O
142H
2O), natisite (Na
2TiOSiO
4), Zorite (claims ETS-4 again, Na
6Ti
5Si
12O
35(OH)
411H
2O), ETS-10 (M
2TiSi
5O
134H
2O, M are Na or K), JLU-1, pharmacosiderite (HM
3Ti
4Si
3O
164H
2O, M=H, K, Cs), GTS-1 (Na
2Ti
2O
3SiO
42H
2O), AM-2 (claims umbite again, K
2Ti
xZr
1-xSi
3O
9H
2O, 0≤x≤1), UND-1 (Na
2.7K
5.3Ti
4Si
12O
364H
2O), penkvilksite (claims penkvilksite-1M again, penkvilksite-2O, or AM-3, Na
4Ti
2Si
8O
225H
2O), nenadkevichite (ANbTi
xSi
2O
7H
2O, 0.8≤x≤17.1, A=Na, Ca), vinagradovite (Na
8Ti
8Si
16O
52) wait that to have chemical formula be A
wM
xTi
ySiO
zNH
2O (A be alkali metal or alkaline-earth metal or hydrogen with and composition thereof, M is a transition metal, 0≤w≤10,0≤x≤5,0＜y≤5,0＜z≤10,0≤n≤20) the Titanium silicate of natural or synthetic preparation.
The preparation method of above-mentioned titanium lithium metasilicate, described Titanium silicate predecessor with two-dimensional layer or three-dimensional framework structure mixes stirring reaction and can periodically change the solubility Aqueous Lithium Salts with the solubility Aqueous Lithium Salts.
The preparation method of above-mentioned titanium lithium metasilicate, described solubility lithium salts can be lithium chloride, lithium oxalate, lithium nitrate, lithium acetate or lithium sulfate.
The method for preparing cathode of lithium battery with above-mentioned titanium lithium metasilicate; Above-mentioned titanium lithium metasilicate and electric conducting material graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio, add suitable quantity of water furnishing pulpous state, stir after 24 hours; It is coated on the Cu film suppresses film forming; Sample vacuumize is 24 hours after the film forming, and dicing is processed lithium ion battery negative then.
Prepare the method for button cell with the above-mentioned lithium ion battery negative that makes, it is under anhydrous argon gas atmosphere, to be anodal with the lithium metal, LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor are electrolyte, are assembled into button cell.
Titanium lithium metasilicate material of the present invention has lower discharge platform, performances such as higher capacitance and fine cycle charging discharge as the negative pole of lithium ion battery.Its discharge platform is about 0.6V, and capacitance is up to 410mAh/g, 1000 undamped phenomenons of charge and discharge cycles.
The invention provides the preparation method of above-mentioned silicon lithium titanate salt electrode material, and silicon lithium titanate salt electrode material of the present invention preparation simple, be easy to get, good reproducibility is one type of superior electrode material.
Description of drawings:
Fig. 1 is charging and discharging curve and the cycle performance curve of this material that is made as behind the button cell.
Embodiment
For clearer explanation the present invention, enumerate following examples, but it there is not any restriction to the present invention.
Embodiment 1:
(1) in beaker, adds 1.75 gram butyl titanates, 6 milliliters of H successively
2O
2, 0.8 gram NaOH, stir half an hour after; Adding 0.8 gram TBAB and 1.2 restrains silicon dioxide, stirs in the autoclave of transferring to polytetrafluoroethylene after 2-3 hour to encapsulate, after heating 10 days under 180 ℃; Cooling; Filter, drying obtains white predecessor, and it is JDF-L1 (claiming AM-1 again) for the identification of phases of X-ray powder diffraction thing.
(2) in round-bottomed flask, add 0.5 gram titan silicate JDF-L1 and 5.0 gram lithium oxalates; Add 150 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; Add 5.0 gram lithium oxalate and 150 ml distilled waters again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product L1-JDF-L1.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.Record its discharge platform about 0.55V, capacitance is up to 333mAh/g, 1000 undamped phenomenons of charge and discharge cycles.
Embodiment 2:
(1) sodium metasilicate of 27.0 grams and the NaOH of 14.76 grams are dissolved in 40 ml waters, add the titanium trichloride solution (15wt%TiCl of 40.30 grams then
3Be dissolved in the hydrochloric acid of 10wt%), after stirring, transfer in the agitated reactor, 230 ℃ of following crystallization 4 days, cooling was filtered, and drying obtains white predecessor, and it is AM-4 for the identification of phases of X-ray powder diffraction thing.
(2) in round-bottomed flask, add 0.5 gram titan silicate AM-4 and 5.0 gram lithium acetates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; Add 5.0 gram lithium acetate and 200 ml distilled waters again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-AM-4.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.The performance of battery is with the battery performance of embodiment one.
Embodiment 3:
(1) 8.0 gram citric acids is dissolved in 100 milliliters the ethylene glycol; Ethylene glycol (30 milliliters) solution that adds 0.672 gram butyl titanate then; Stir after 3 hours, add 0.822 gram tetraethoxysilane, stirred 1 hour; Add ethylene glycol (30 milliliters) solution of 0.913 gram barium acetate then, stir and obtain vitreosol after 2 hours.Colloidal sol 150 ℃ of following ageings 2 days, is obtained the resin-like solid.The resin-like solid is placed Muffle furnace, 900 ℃ of following roastings 12 hours, obtain white predecessor, it is fresnoite for the identification of phases of X-ray powder diffraction thing.
(2) in round-bottomed flask, add 0.5 gram titan silicate fresnoite and 5.0 gram lithium acetates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; Add 5.0 gram lithium acetate and 200 ml distilled waters again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-fresnoite.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.Record its discharge platform about 0.55V, capacitance is up to 410mAh/g.
Embodiment 4:
(1) 9.6 gram NaOH is dissolved in 45 ml waters, adds 0.18 gram SiO 2 powder and 2.85 gram titanium tetrachlorides then, be heated to the back cooling of boiling; Continue to stir after 1 hour, transfer in the agitated reactor, 200 ℃ of following crystallization 24 hours; Cooling; Filter, drying obtains white predecessor, and it is natisite for the identification of phases of X-ray powder diffraction thing.
(2) in round-bottomed flask, add 0.5 gram titan silicate natisite and 5.0 gram lithium acetates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; Add 5.0 gram lithium acetate and 200 ml distilled waters again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-natisite.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.The performance of battery is with the battery performance of embodiment three.
Embodiment 5:
(1) in beaker, adds 3.2 gram NaOH and 15 ml waters successively, add butyl titanate 4.0 grams and H after the stirring and dissolving
2O
2(8 milliliters) add 4-propyl bromide (1.6 gram) and SiO again
2(2.4 gram) after stirring, transferred in the agitated reactor, and at 180 ℃ of following crystallization 3-5 days, cooling was filtered, and drying obtains white predecessor, and it is ETS-4 (claiming Zorite again) for the identification of phases of X-ray powder diffraction thing.
(2) in round-bottomed flask, add 0.5 gram titan silicate ETS-4 and 5.0 gram lithium acetates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; 5.0 gram lithium acetate and 200 ml distilled waters that add again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-ETS-4.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.Record its discharge platform about 0.60V, capacitance reaches 255mAh/g, 500 undamped phenomenons of charge and discharge cycles.
Embodiment 6:
(1) in beaker, adds successively in 0.27 gram NaOH and 12 ml waters, add butyl titanate (98%) 5.1 gram then, add (25%) 2.5 milliliter of TMAH and SiO again
2(0.6 gram) after stirring, is transferred in the agitated reactor, and 180 ℃ of following crystallization 15 days, cooling was filtered, and drying obtains white predecessor, and it is penkvilksite-1M for the identification of phases of X-ray powder diffraction thing.
(2) in round-bottomed flask, add 0.5 gram titan silicate penkvilksite-1M and 0.66 gram lithium nitrate; Add 150 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; 5.0 gram lithium nitrate and 150 ml distilled waters that add again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-penkvilksite.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are assembled into CR-2032 type button cell for electrolyte is electrolyte.The performance of battery is with the battery performance of embodiment five.
Embodiment 7:
(1) in beaker, adds 0.25 gram NaOH and 12 ml waters successively, add butyl titanate 1.8 grams after the stirring and dissolving, add TBAH (3 milliliters) and SiO again
2(1.25 gram) after stirring, transferred in the agitated reactor, and at 200 ℃ of following crystallization 8-10 days, cooling was filtered, and drying obtains white predecessor, and it is JLU-1 for the identification of phases of X-ray powder diffraction thing.
(2) in round-bottomed flask, add 0.5 gram titan silicate JLU-1 and 5.0 gram lithium nitrates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; Add 5.0 gram lithium acetate and 200 ml distilled waters again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-JLU-1.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.Record its discharge platform about 0.50V, capacitance reaches 252mAh/g.
Embodiment 8:
(1) in beaker, adds 6.43 gram NaOH, 4.20 gram KOH and 10 ml waters successively, add the 32.03 gram Ludox (Na of 7.2wt% after the stirring and dissolving
2The SiO of O and 25.7wt%
2), add 4.75 gram titanium tetrachloride and 10 milliliters of H again
2O after stirring, transfers in the agitated reactor, and 220 ℃ of following crystallization 36 hours, cooling was filtered, and drying obtains white predecessor, and it is ETS-10 for the identification of phases of X-ray powder diffraction thing.
(2) in round-bottomed flask, add 0.5 gram titan silicate ETS-10 and 5.0 gram lithium acetates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; Add 5.0 gram lithium acetate and 200 ml distilled waters again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-ETS-10.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.The performance of battery is with the battery performance of embodiment seven.
Embodiment 9:
(1) with 2.11 gram TiCl
4Add in the hydrochloric acid of 7.9 milliliters of 15wt%, add 25 milliliters of hydrogenperoxide steam generators (30wt%) then, add 8.9 gram NaOH then, filter, with distilled water washing, drying.The gained solid is dissolved in 100 milliliters of 10M sodium hydrate aqueous solutions, adds 33.4 gram Ludox (Ludox HS-40) again, stir, 60 ℃ of ageings, filtration, washing, drying obtain unformed predecessor.9.0 gram predecessors are placed the sodium hydroxide solution of 30 milliliters of 1M, transfer in the agitated reactor, 160 ℃ of following crystallization 4 days, cooling was filtered, and drying obtains white predecessor, and it is pharmacosiderite for the identification of phases of X-ray powder diffraction thing.
(2) in round-bottomed flask, add 0.5 gram titan silicate pharmacosiderite and 5.0 gram lithium acetates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; Add 5.0 gram lithium acetate and 200 ml distilled waters again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-pharmacosiderite.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.The performance of battery is with the battery performance of embodiment seven.
Embodiment 10:
(1) in beaker, 5.30 gram butyl titanates is mixed with 3.33 gram tetraethoxysilanes, add the sodium hydroxide solution of 26 milliliters of 6.32M then, after stirring; Transfer in the agitated reactor; 170 ℃ of following crystallization 8 days, cooling was filtered; Drying obtains white predecessor, and it is GTS-1 for the identification of phases of X-ray powder diffraction thing.
(2) in round-bottomed flask, add 0.5 gram titan silicate GTS-1 and 5.0 gram lithium acetates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; Add 5.0 gram lithium acetate and 200 ml distilled waters again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-GTS-1.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.The performance of battery is with the battery performance of embodiment seven.
Embodiment 11:
(1) in beaker, add 4.16 gram SiO 2 powders, 8.50 gram potassium hydroxide, 2.74 gram potassium chloride and 30 ml waters after mixing, add 11.42 gram titanium trichloride hydrochloric acid solution (23.5wt%TiCl
3, remain hydrochloric acid into 5.9wt%), after stirring, transfer in the agitated reactor, 230 ℃ of following crystallization 4 days, cooling was filtered, and drying obtains white predecessor, and it is AM-2 (claiming umbite again) for the identification of phases of X-ray powder diffraction thing.
(2) in round-bottomed flask, add 0.5 gram titan silicate AM-2 and 5.0 gram lithium acetates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; Add 5.0 gram lithium acetate and 200 ml distilled waters again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-AM-2.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.The performance of battery is with the battery performance of embodiment seven.
Embodiment 12:
(1) in beaker, add 1.44 gram butyl titanates successively, 2.2 gram distilled water and 0.7 gram ethanol are processed titanium colloidal sol, add a certain amount of NaOH and TMAH again; After stirring, 220 ℃ of following roastings 24 hours, cooling; Filter, drying obtains predecessor vinogradovite.
(2) in round-bottomed flask, add 0.5 gram titan silicate vinogradovite and 5.0 gram lithium acetates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; 5.0 gram lithium acetate and 200 ml distilled waters that add again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-vinogradovite.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.The performance of battery is with the battery performance of embodiment seven.
Embodiment 13:
(1) in beaker, adds 10.06 gram Ludox (30wt%) successively, 15.05 gram water, 2.3 gram NaOH; 0.96 the gram potassium fluoride, 0.38 gram potassium chloride, 0.46 gram sodium chloride; 4.63 gram titanium trichloride solution (15wt%) restrains niobium pentaoxide with 0.15, after stirring, 230 ℃ of following crystallization are 7 days in agitated reactor; Cooling is filtered, and drying obtains predecessor Nenadkevichite.
(2) in round-bottomed flask, add 0.5 gram titan silicate nenadkevichite and 5.0 gram lithium acetates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; 5.0 gram lithium acetate and 200 ml distilled waters that add again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-nenadkevichite.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.The performance of battery is with the battery performance of embodiment seven.
Embodiment 14:
(1) in beaker, add 10.0 gram Ludox (30wt%) successively, 0.8 gram titanium dioxide, 1.8 gram NaOH, 1.72 gram potassium hydroxide, 10 gram water, after stirring, 200 ℃ of following crystallization are 3 days in agitated reactor, and cooling is filtered, and drying obtains predecessor UND-1.
(2) in round-bottomed flask, add 0.5 gram titan silicate UND-1 and 5.0 gram lithium acetates; Add 200 ml distilled waters again; Heated and stirred was filtered after 24 hours under 100 ℃ of oil baths, added solid matter in the round-bottomed flask again; 5.0 gram lithium acetate and 200 ml distilled waters that add again, heated and stirred is 24 hours under 100 ℃ of oil baths.Filtering drying after repeating 2 times so again obtains product Li-UND-1.
(3) product, graphite, adhesive carboxymethyl cellulose disodium is even with 8: 1: 1 ground and mixed of mass ratio; Add suitable quantity of water furnishing pulpous state, stir after 24 hours and take out, it is coated on the Cu film suppresses film forming; After the membrane sample vacuumize 24 hours, dicing is processed the lithium ion negative pole.Under anhydrous argon gas atmosphere be anodal with the lithium metal, 1mol/L LiPF
6Be electrolyte, ethylene carbonate, dimethyl carbonate mixed liquor (mass ratio 1: 1) are electrolyte, are assembled into CR-2032 type button cell.The performance of battery is with the battery performance of embodiment seven.
Claims (9)
1. titanium lithium metasilicate as electrode material of lithium battery is characterized in that: it is a Titanium silicate predecessor with two-dimensional layer or three-dimensional framework structure through making the titanium lithium metasilicate of electrode material of lithium battery with lithium ion ion-exchange.
2. the titanium lithium metasilicate as electrode material of lithium battery according to claim 1 is characterized in that: described Titanium silicate predecessor with two-dimensional layer or three-dimensional framework structure is JDF-L1, fresnoite, AM-4, natisite, Zorite, ETS-10, JLU-1, pharmacosiderite, GTS-1, AM-2, UND-1, penkvilksite, nenadkevichite or vinagradovite.
3. the titanium lithium metasilicate as electrode material of lithium battery according to claim 2 is characterized in that: described Titanium silicate predecessor with two-dimensional layer or three-dimensional framework structure is natural or synthetic preparation.
4. method for preparing the described titanium lithium metasilicate of claim 1; It is characterized in that: it is that the Titanium silicate predecessor with two-dimensional layer or three-dimensional framework structure is mixed with the solubility Aqueous Lithium Salts; At 100 ℃ of stirring reaction 24-100 hours, promptly get white powder, as the titanium lithium metasilicate of electrode material of lithium battery.
5. the preparation method of titanium lithium metasilicate according to claim 4 is characterized in that: described Titanium silicate predecessor with two-dimensional layer or three-dimensional framework structure is JDF-L1, fresnoite, AM-4, natisite, Zorite, ETS-10, JLU-1, pharmacosiderite, GTS-1, AM-2, UND-1, penkvilksite, nenadkevichite or vinagradovite.
6. the preparation method of titanium lithium metasilicate according to claim 5 is characterized in that: described Titanium silicate predecessor with two-dimensional layer or three-dimensional framework structure is natural or synthetic preparation.
7. the preparation method of titanium lithium metasilicate according to claim 4 is characterized in that: described Titanium silicate predecessor with two-dimensional layer or three-dimensional framework structure mixes stirring reaction with the solubility Aqueous Lithium Salts and periodically changes the solubility Aqueous Lithium Salts.
8. the preparation method of titanium lithium metasilicate according to claim 4 is characterized in that: described solubility lithium salts is lithium chloride, lithium oxalate, lithium nitrate, lithium acetate or lithium sulfate.
9. the described application of titanium lithium metasilicate in the preparation lithium cell cathode material of claim 1 as electrode material of lithium battery.
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| CN105024070A (en) * | 2015-06-16 | 2015-11-04 | 中南大学 | Preparation method of lithium titanium silicate anode material for lithium ion battery |
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| CN105226281A (en) * | 2015-10-20 | 2016-01-06 | 复旦大学 | The titanium silicate lithium titanate cathode material of lithium ion battery and preparation method and application |
| CN106573787A (en) * | 2014-07-18 | 2017-04-19 | 东曹株式会社 | Composition including silicotitanate having sitinakite structure, and production method for same |
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| CN104810513A (en) * | 2015-03-31 | 2015-07-29 | 中南大学 | Lithium ion battery cathode material and preparation method thereof |
| CN104953099A (en) * | 2015-06-16 | 2015-09-30 | 中南大学 | Lithium ion battery anode material and preparation method thereof |
| CN105024070A (en) * | 2015-06-16 | 2015-11-04 | 中南大学 | Preparation method of lithium titanium silicate anode material for lithium ion battery |
| CN105024069A (en) * | 2015-06-16 | 2015-11-04 | 中南大学 | Li2TiSiO5/C composite anode material for lithium-ion battery and preparation method of Li2TiSiO5/C composite anode material |
| CN105024070B (en) * | 2015-06-16 | 2017-08-25 | 中南大学 | A kind of preparation method of titanium silicate lithium ion battery negative material |
| CN105024069B (en) * | 2015-06-16 | 2017-10-10 | 中南大学 | A kind of lithium ion battery Li2TiSiO5/ C composite negative pole materials and preparation method thereof |
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| CN112467096A (en) * | 2020-10-30 | 2021-03-09 | 安普瑞斯（南京）有限公司 | Negative electrode material, preparation method thereof, electrode and secondary battery |
| CN112467096B (en) * | 2020-10-30 | 2022-09-23 | 安普瑞斯（南京）有限公司 | Negative electrode material, preparation method thereof, electrode and secondary battery |
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