CN103730649B - A kind of preparation method of lithium battery carbon cladding lithium titanate anode material - Google Patents
A kind of preparation method of lithium battery carbon cladding lithium titanate anode material Download PDFInfo
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- CN103730649B CN103730649B CN201410017827.3A CN201410017827A CN103730649B CN 103730649 B CN103730649 B CN 103730649B CN 201410017827 A CN201410017827 A CN 201410017827A CN 103730649 B CN103730649 B CN 103730649B
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- lithium titanate
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 114
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 238000005253 cladding Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000010405 anode material Substances 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011268 mixed slurry Substances 0.000 claims description 16
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 16
- 239000012989 trithiocarbonate Substances 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229910052596 spinel Inorganic materials 0.000 claims description 10
- 239000011029 spinel Substances 0.000 claims description 10
- 229910009866 Ti5O12 Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000010550 living polymerization reaction Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 modified lithium titanate Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses the preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, this method uses living polymerization to prepare the polymer that molecular weight is controlled, and carry out firing after ball milling mixes with the raw material of lithium titanate, obtain the lithium titanate material of coated with conductive carbon-coating, the optional monomer of polymerization that the present invention uses is in extensive range, the polymer of different carbon chain lengths is can get by regulation proportioning raw materials, and carbon chain length distribution is uniform, the carbon finally given is coated with the sourest lithium material performance stable homogeneous, and the lithium titanate material obtained is at 1C(1C=175mA/g) initial charge specific capacity reaches more than 160mAh/g under multiplying power, more than 90% is kept through 800 circulation volumes.
Description
Technical field
The present invention relates to the preparation method of a kind of lithium ion battery negative material, particularly relate to the preparation method of a kind of lithium battery carbon cladding lithium titanate anode material.
Background technology
Lithium ion battery is that a kind of Novel rechargeable battery, its energy density per unit volume and specific energy are high, can fill and pollution-free, is referred to as " the most promising electrochmical power source " by people, develop very fast.Lithium ion battery has been widely used in the portable type electronic product power supplys such as mobile phone, laptop computer and video camera, and is gradually applied to hybrid electric vehicle, pure electric vehicle and regenerative resource power station as electrokinetic cell and accumulation power supply.The lithium ion battery negative material of commercialization at present is mainly graphitized carbon material, but there is the problem that safety is poor.
Spinel type lithium titanate (Li4Ti5O12) lithium ion battery negative material having Commercial Prospect is become with its outstanding security feature and long circulation life.Li4Ti5O12As negative material, during lithium ion is de-/embedding, crystal structure can keep the stability of height, and makes it have excellent cycle performance and stable discharge voltage；There is of a relatively high electrode potential so that this electrode material can use in the burning voltage interval of most liquid electrolyte, thus avoids the generation of electrolyte decomposition phenomenon or protecting film；Prepare raw material (TiO2、Li2CO3Or LiOH H2O etc.) originate and also relatively enrich.But this material intrinsic conductivity is low, become the key factor of its development of restriction.
Li4Ti5O12Electron conduction is very poor, belongs to typical insulator, will cause serious polarization in electrochemical reaction process, even produces amount of heat, the most unfavorable to electrode performance.Certainly, by doping/cladding etc. to Li4Ti5O12Modification, leads performance to raising electrode significant.
Guerfi etc. with polymer as carbon source, carry out wet mixing with acetone and water for solvent, the lithium titanate of the carbon that is prepared for adulterating, it is thus achieved that preferably chemical property (A. Guerfi, P. Charest, Power Sources 2004,126,163-168.).And United States Patent (USP) US 2004/0202934A1 discloses employing several kinds of carbon source and includes that white carbon black, polyol, polyethylene glycol etc. are modified to lithium titanate.But use living polymerization to prepare carbon source and the method that lithium titanate is modified is had no report.
CN
102593444A discloses preparation method and the product thereof of a kind of carbon cladding lithium titanate.First it be dispersed in deionized water water with lithium titanate and cetyl trimethylammonium bromide, add resorcinol, formaldehyde and sodium carbonate, reflow treatment afterproduct washs, is dried to obtain presoma, finally presoma is calcined under an inert atmosphere and obtain carbon cladding lithium titanate, improve the electric conductivity of lithium titanate so that it is circulation and high rate performance are all greatly improved.
CN
102569767A discloses a kind of polymer composite lithium titanate electrode and preparation method thereof.First this invention prepares oxidizing agent solution A, the protonic acid solution B of prepared polymer monomer；Joining in solution B by lithium titanate powder again, then solution A be progressively added drop-wise in solution B, dispersed with stirring obtains resulting polymer composite lithium titanate electrode material after reacting.
In above-mentioned two patents, the method for modifying to lithium titanate material all uses the electric conductivity adding polymer to improve lithium titanate, but the type of polymer that method therefor obtains is single, its molecular chain length is uncontrollable and different in size, stable performance cannot improve the effect of electrical conductivity for modified conductive materials in the modified lithium titanate material finally given.Meanwhile, in above-mentioned two patents, the preparation method for modified polymer is higher to equipment and environmental requirement, CN
Polymerization used by 102593444A uses reflux, and reactor is more complicated, need to be by backflow tower reactor；Polymerization used by CN 102569767A uses monomer only to limit conducting polymer monomer, and need to use protonic acid doping, and is slowly added dropwise oxidant, and operation is more complicated, it is difficult to industrialization produces continuously.
Summary of the invention
The invention provides the preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, this method uses living polymerization to prepare the polymer that molecular weight is controlled, and carry out firing after ball milling mixes with the raw material of lithium titanate, obtain the lithium titanate material of coated with conductive carbon-coating, the optional monomer of polymerization that the present invention uses is in extensive range, be can get the polymer of different carbon chain lengths by regulation proportioning raw materials, and carbon chain length distribution is uniform, the carbon finally given is coated with the sourest lithium material performance stable homogeneous.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is:
A kind of preparation method of lithium battery carbon cladding lithium titanate anode material, it is characterised in that: comprise the following steps:
(1) polymer monomer, azo-initiator and trithiocarbonate are dissolved in oxolane and are configured to solution, 70-90 in nitrogen atmosphereoReact 5-10 hour at a temperature of C, obtain mixed solution, wherein, polymer monomer: azo-initiator: the mol ratio of trithiocarbonate is 100:0.5-1:
0.01-1, polymer monomer is 1:1-2 with the volume ratio of oxolane；
(2) mixed solution that step (1) obtains is precipitated in precipitant obtain polymeric carbon source；
(3) lithium ion and titanium ion mol ratio Li are pressed+: Ti+=0.8:1 weighs lithium-containing compound and titanium-containing oxide, and weigh, by the 5%-20% of lithium-containing compound Yu the mass fraction of titanium-containing oxide gross weight, the polymeric carbon source that step (2) obtains, adding deionized water is dispersant ball milling 4-8 hour in ball grinder, it is thus achieved that the mixed slurry of mix homogeneously；
(4) mixed slurry step (3) obtained, is delivered to spray dryer and carries out granulating and drying, it is thus achieved that dry mixed powder；
(5) by the presoma powder body high-temperature roasting 8-16 in an inert atmosphere of step (4) granulating and drying hour, it is thus achieved that the spinel type lithium titanate material Li of carbon cladding4Ti5O12。
The preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, roasting process two step in preferred steps (5) is carried out, and is first according to 1-10oThe programming rate of C/min, is increased to 400 from room temperatureoC-600oC, and keep 4-8 hour；Then according to the programming rate of 1-10 DEG C/min, temperature is increased to 700oC-900oC, and keep 4-8 hour.
The preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, preferably azo-initiator is azo-bis-isobutyl cyanide or 2,2'-Azobis(2,4-dimethylvaleronitrile).
The preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, preferred polymers monomer is any one in acrylic acid, methacrylic acid, acrylic acid methyl ester., methyl methacrylate, ethyl methacrylate, styrene.
A kind of preparation method of lithium battery carbon cladding lithium titanate anode material, any one during preferably precipitant is methanol, ethanol, petroleum ether.
A kind of lithium battery carbon cladding lithium titanate anode material preparation method, during preferably lithium-containing compound includes lithium carbonate, Lithium hydrate, lithium oxalate, lithium acetate one or several arbitrarily than mixture.
A kind of lithium battery carbon cladding lithium titanate anode material preparation method, during preferably titanium-containing oxide includes rutile titanium dioxide, anatase titanium dioxide one or several arbitrarily than mixture.
The preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, in step (4), described granulating and drying is particularly as follows: being spray-dried inlet temperature is 150
oC -250 oC, outlet temperature is 100 oC -150 oC, charging rate is 0.01-0.1L/min.
A kind of lithium battery carbon cladding lithium titanate anode material preparation method, during preferably noble gas includes helium, argon, nitrogen one or several arbitrarily than mixture.
The invention have the advantages that
Compared with prior art, the manufacture method of carbon of the present invention cladding lithium titanate material has the advantages that
1, the present invention obtains polymeric carbon source by living polymerization, it is only necessary to replace polymer monomer be obtained with different carbon source, polymer molecular weight is controlled, and molecular weight distribution is little, it is thus achieved that carbon cladding lithium titanate material surface carbon chain length homogeneous controlled.
2, invention uses carbon cladding modified to lithium titanate material, it is thus achieved that lithium titanate material at 1C(1C=175mA/g) initial charge specific capacity reaches more than 160mAh/g under multiplying power, keeps more than 90% through 500 circulation volumes.And lithium titanate material prepared by existing method is at 1C(1C=175mA/g) initial charge specific capacity generally only reaches 150mAh/g under multiplying power, generally remain less than 80% through 500 circulation volumes.
3, the present invention uses two-stage roasting technique, and lithium titanate crystallite dimension is little, and energy resource consumption is few, low for equipment requirements, easily realizes industrialized production.
4, the present invention uses closed reactor, and polymer monomer is without with protonic acid doping, and technique is relatively easy, it is adaptable to industrialization produces continuously.
Accompanying drawing explanation
Fig. 1 is lithium battery 800 cycle charge-discharge curves of graphite-doping lithium titanate anode material 1C multiplying power of the present invention.
Detailed description of the invention
Embodiment 1
The preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, is prepared by following steps:
1) polymer monomer methacrylic acid, azo-initiator azo-bis-isobutyl cyanide and trithiocarbonate are dissolved in oxolane and are configured to mixed solution, 70-90 in nitrogen atmosphereoReacting 5-10 hour at a temperature of C, this course of reaction is carried out in closed reactor.The mol ratio of the most each mixture is, methacrylic acid: azo-bis-isobutyl cyanide: trithiocarbonate=100:0.5-1:
0.01-1, polymer monomer with the volume ratio of solvent is, polymer monomer: oxolane=1:1-2；Polymerization rate described in this step raises with reaction temperature and accelerates；Made polymer molecular weight increases with the content of trithiocarbonate in reaction raw materials and reduces, and reduces with the increase in response time；Solvent for use preferably can be completely dissolved the minimum of added solid matter.
2) solution step 1) obtained precipitates in methanol, and then filtration drying obtains polymer.
3) lithium ion and titanium ion mol ratio Li are pressed+: Ti+=0.8:1 weighs lithium-containing compound lithium carbonate and titanium-containing oxide anatase titanium dioxide, and weigh, by the 5%-20% of lithium carbonate Yu the mass fraction of anatase titanium dioxide gross weight, the polymer that (step 2) obtains, adding deionized water is dispersant ball milling 4-8 hour in ball grinder, it is thus achieved that the mixed slurry of mix homogeneously；Lithium ion in this step and titanium ion mol ratio are with lithium, the conversion of titanium mol ratio in product lithium titanate；Lithium titanate material electrical conductivity increases with polymer content and increases, and specific capacity increases with polymer content and reduces；Described Ball-milling Time becomes on the basis of uniform sizing material by mixture, and those skilled in the art can select described Ball-milling Time voluntarily according to this area knowledge.
4) mixed slurry step 3) obtained, mixed slurry is delivered to spray dryer and carries out granulating and drying, it is thus achieved that dry mixed powder；
5) by the presoma powder body of step 4) granulating and drying in a nitrogen environment at 400-900oC roasting temperature 8-16 hour, it is thus achieved that the spinel type lithium titanate material Li of carbon cladding4Ti5O12.The perfect crystalline degree of the lithium titanate material in this step improves with the rising of sintering temperature, improves with the increase of roasting time；The granular size of described lithium titanate material increases with the rising of temperature, increases with the increase of roasting time.
Embodiment 2
The preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, is prepared by following steps:
1) polymer monomer methacrylic acid, azo-initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) and trithiocarbonate are dissolved in oxolane and are configured to mixed solution, in nitrogen atmosphere 80oReacting 5 hours at a temperature of C, this course of reaction is carried out in closed reactor.The mol ratio of the most each mixture is, methacrylic acid: azo-bis-isobutyl cyanide: trithiocarbonate=100:
1:0.5, polymer monomer with the volume ratio of solvent is, polymer monomer: oxolane=1:2；
2) solution step 1) obtained precipitates in methanol, and then filtration drying obtains polymer.
3) lithium ion and titanium ion mol ratio Li are pressed+: Ti+=0.8:1 weighs lithium-containing compound lithium carbonate and titanium-containing oxide anatase titanium dioxide, and weigh, with the 5% of the mass fraction of anatase titanium dioxide gross weight, the polymer that (step 2) obtains by lithium carbonate, adding deionized water is dispersant ball milling 4 hours in ball grinder, it is thus achieved that the mixed slurry of mix homogeneously；
4) mixed slurry that step 3) obtains being delivered to spray dryer, being spray-dried inlet temperature is 150
oC -250 oC, outlet temperature is 100 oC -150 oC, charging rate is 0.01-0.1L/min, carries out granulating and drying；The inlet temperature of this step is more than 100 with charging rate with outlet temperatureoC is criterion, and those skilled in the art can select voluntarily according to the viscosity of slurry described in the knowledge reference of this area.
5) by the presoma powder body high-temperature roasting in a nitrogen environment of step 4) granulating and drying, roasting process uses two-stage roasting.It is first according to 1-10oThe programming rate of C/min, is increased to 400 from room temperatureoC-600oC, and keep 4-8 hour；Then according to the programming rate of 1-10 DEG C/min, temperature is increased to 700oC-900oC, and keep 4-8 hour；The spinel type lithium titanate material Li of the carbon cladding obtained4Ti5O12.Two-stage roasting in this step completes in same high temperature reaction stove, and first paragraph roasting makes lithium-containing compound form oxide, and second segment roasting forms lithium titanate crystallization, using two-stage roasting technique, lithium titanate crystallite dimension is little, and energy resource consumption is few, low for equipment requirements, easily realize industrialized production.
Embodiment 3
The preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, is prepared by following steps:
1) polymer monomer methyl methacrylate, initiator azo-bis-isobutyl cyanide and trithiocarbonate are dissolved in oxolane and are configured to solution, in nitrogen atmosphere 70oReact 10 hours at a temperature of C.Wherein mol ratio is, methyl methacrylate: azo-bis-isobutyl cyanide: trithiocarbonate=100:
0.5:0.1, methyl methacrylate: oxolane=1:1.5；
2) solution step 1) obtained precipitates in methanol, and then filtration drying obtains polymer；
3) lithium ion and titanium ion mol ratio Li are pressed+: Ti+=0.8:1 weighs lithium-containing compound Lithium hydrate and titanium-containing oxide rutile titanium dioxide, and weigh, with the 10% of the mass fraction of titanium-containing oxide gross weight, the polymer that (step 2) obtains by lithium-containing compound, adding deionized water is dispersant ball milling 6 hours in ball grinder, it is thus achieved that the mixed slurry of mix homogeneously；
4) mixed slurry step 3) obtained, is delivered to spray dryer, and being spray-dried inlet temperature is 200
oC, outlet temperature is 125
oC, charging rate is 0.1L/min, carries out granulating and drying；
5) by the presoma powder body high-temperature roasting in a nitrogen environment of step 4) granulating and drying, roasting process uses two-stage roasting, is first according to 5oThe programming rate of C/min, is increased to 450 from room temperatureoC, and keep 5 hours；Then according to the programming rate of 5 DEG C/min, temperature is increased to 850oC, and keep 7 hours；The spinel type lithium titanate material Li of the carbon cladding obtained4Ti5O12。
Embodiment 4
The preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, is prepared by following steps:
1) polymer monomer styrene, initiator azo-bis-isobutyl cyanide and trithiocarbonate are dissolved in oxolane and are configured to solution, in nitrogen atmosphere 90oReact 8 hours at a temperature of C.Wherein mol ratio is monomer: initiator: trithiocarbonate=100:
0.5:1, monomer is monomer with the volume ratio of solvent: oxolane=1:1；
2) solution step 1) obtained precipitates in methanol, and then filtration drying obtains polymer；
3) lithium ion and titanium ion mol ratio Li are pressed+: Ti+=0.8:1 weighs lithium-containing compound lithium acetate and titanium-containing oxide anatase titanium dioxide, and weigh, with the 15% of the mass fraction of titanium-containing oxide gross weight, the polymer that (step 2) obtains by lithium-containing compound, adding deionized water is dispersant ball milling 8 hours in ball grinder, it is thus achieved that the mixed slurry of mix homogeneously；
4) mixed slurry step 3) obtained, is delivered to spray dryer, and being spray-dried inlet temperature is 150
oC, outlet temperature is 100
oC, charging rate is 0.01L/min, carries out granulating and drying；
5) by the presoma powder body high-temperature roasting in a nitrogen environment of step 4) granulating and drying, roasting process uses two-stage roasting.It is first according to 1oThe programming rate of C/min, is increased to 550 from room temperatureoC, and keep 4 hours；Then according to the programming rate of 1 DEG C/min, temperature is increased to 750oC, and keep 6 hours；The spinel type lithium titanate material Li of the carbon cladding obtained4Ti5O12。
Embodiment 5
The preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, is prepared by following steps:
1mol ethyl acrylate, 0.005mol initiator azo-bis-isobutyl cyanide and 0.01mol trithiocarbonate are dissolved in 100ml oxolane and are configured to solution, in nitrogen atmosphere 80oReacting 8 hours at a temperature of C, the solution obtained precipitates in petroleum ether and obtains polymer.Weighing 1mol lithium carbonate and 2.5mol anatase titanium dioxide, add the polymer 13.68g that step (2) obtains, adding deionized water is dispersant ball milling 8 hours in ball grinder, it is thus achieved that the mixed slurry of mix homogeneously is delivered to spray dryer.Being spray-dried inlet temperature is 150 oC, outlet temperature is 100 oC, charging rate is 0.05L/min, the high-temperature roasting in a nitrogen environment of the powder body of granulating and drying.It is first according to 10oThe programming rate of C/min, is increased to 550 from room temperatureoC, and keep 4 hours；Then according to the programming rate of 10 DEG C/min, temperature is increased to 750oC, and keep 6 hours；The spinel type lithium titanate material Li of the carbon cladding obtained4Ti5O12。
Embodiment 6
The preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, is prepared by following steps:
1mol acrylic acid, 0.005mol initiator azo-bis-isobutyl cyanide and 0.001mol trithiocarbonate are dissolved in 80ml oxolane and are configured to solution, in nitrogen atmosphere 85oReacting 10 hours at a temperature of C, the solution obtained precipitates in methanol and obtains polymer.Weighing 1mol Lithium hydrate and 1.25mol anatase titanium dioxide, add the polymer 12.38g that step (2) obtains, adding deionized water is dispersant ball milling 6 hours in ball grinder, it is thus achieved that the mixed slurry of mix homogeneously is delivered to spray dryer.Being spray-dried inlet temperature is 150 oC, outlet temperature is 100 oC, charging rate is 0.1L/min, the high-temperature roasting in a nitrogen environment of the powder body of granulating and drying.It is first according to 3oThe programming rate of C/min, is increased to 500 from room temperatureoC, and keep 5 hours；Then according to the programming rate of 3 DEG C/min, temperature is increased to 900oC, and keep 5 hours；The spinel type lithium titanate material Li of the carbon cladding obtained4Ti5O12。
Embodiment 7
The preparation method of a kind of lithium battery carbon cladding lithium titanate anode material, is prepared by following steps:
1mol ethyl methacrylate, 0.005mol initiator azo-bis-isobutyl cyanide and 0.05mol trithiocarbonate are dissolved in 100ml oxolane and are configured to solution, in nitrogen atmosphere 90oReacting 6 hours at a temperature of C, the solution obtained precipitates in ethanol and obtains polymer.Weighing 1mol lithium acetate and 1.25mol anatase titanium dioxide, add the polymer 30.28g that step (2) obtains, adding deionized water is dispersant ball milling 5 hours in ball grinder, it is thus achieved that the mixed slurry of mix homogeneously is delivered to spray dryer.Being spray-dried inlet temperature is 200 oC, outlet temperature is 125 oC, charging rate is 0.1L/min, the high-temperature roasting in a nitrogen environment of the powder body of granulating and drying.It is first according to 3oThe programming rate of C/min, is increased to 550 from room temperatureoC, and keep 5 hours；Then according to the programming rate of 3 DEG C/min, temperature is increased to 850oC, and keep 5 hours；The spinel type lithium titanate material Li of the carbon cladding obtained4Ti5O12。
Embodiment 8
Electrode material, conductive agent white carbon black and bonding agent Kynoar (PVDF) 8:1:1 in mass ratio mixing embodiment 3 prepared, adds N-Methyl pyrrolidone (NMP) and is modulated into slurry, and be coated uniformly on Copper Foil, 100
oCWith tablet machine, pole piece compacting is uniformly obtained pole piece to be measured after vacuum is dried 12 hours.With lithium sheet for electrode, electrolyte is 1mol/L concentration LiPF6The solution of ethyl carbonate ester (EC)+dimethyl carbonate (DMC) (volume ratio 1:1), barrier film uses model to be the battery diaphragm of celgard2325, is assembled into CR2032 type button cell in the glove box of argon gas atmosphere.The battery that the negative material of example 2 preparation is filled does constant current charge-discharge test in 1-2.5V voltage range, at 1C(175mA/g) under multiplying power, first discharge specific capacity is 163.8mAh/g, and initial charge specific capacity is 160.2mAh/g, and first charge-discharge efficiency is 97.8%；After circulating 800 times, its specific discharge capacity is 147.4mAh/g, and charge specific capacity is 147.3mAh/g.
Embodiment 9
Electrode material embodiment 5 prepared is assembled into button heart test battery according to method described in example 7, constant current charge-discharge test is done in 1-2.5V voltage range, at 1C(175mA/g) under multiplying power, its first charge-discharge curve is as shown in Figure 1, first discharge specific capacity is 164.8mAh/g, initial charge specific capacity is 153.8mAh/g, and first charge-discharge efficiency is 93.3%；After circulating 800 times, its specific discharge capacity is 163.4mAh/g, and charge specific capacity is 163.3mAh/g.
Claims (7)
1. the lithium battery preparation method of carbon cladding lithium titanate anode material, it is characterised in that: comprise the following steps:
(1) polymer monomer, azo-initiator and trithiocarbonate are dissolved in oxolane and are configured to solution, 70-90 in nitrogen atmosphereoReacting 5-10 hour at a temperature of C, obtain mixed solution, wherein, polymer monomer: azo-initiator: the mol ratio of trithiocarbonate is 100:0.5-1:0.01-1, polymer monomer is 1:1-2 with the volume ratio of oxolane；
(2) mixed solution that step (1) obtains is precipitated in precipitant obtain polymeric carbon source；
(3) lithium ion and titanium ion mol ratio Li are pressed+: Ti+=0.8:1 weighs lithium-containing compound and titanium-containing oxide, and weigh, by the 5%-20% of lithium-containing compound Yu the mass fraction of titanium-containing oxide gross weight, the polymeric carbon source that step (2) obtains, adding deionized water is dispersant ball milling 4-8 hour in ball grinder, it is thus achieved that the mixed slurry of mix homogeneously；
(4) mixed slurry that step (3) obtains is delivered to spray dryer and carries out granulating and drying, it is thus achieved that dry mixed powder；Described granulating and drying is particularly as follows: being spray-dried inlet temperature is 150 oC -250 oC, outlet temperature is 100
oC -150 oC, charging rate is 0.01-0.1L/min；
(5) by the presoma powder body of step (4) granulating and drying in an inert atmosphere, at 400-900oC roasting temperature 8-16 hour, it is thus achieved that the spinel type lithium titanate material Li of carbon cladding4Ti5O12；Described roasting process two step, is first according to 1-10oThe programming rate of C/min, is increased to 400 from room temperatureoC-600oC, and keep 4-8 hour；Then according to the programming rate of 1-10 DEG C/min, temperature is increased to 700oC-900oC, and keep 4-8 hour.
The preparation method of a kind of lithium battery carbon the most according to claim 1 cladding lithium titanate anode material, it is characterised in that: described azo-initiator is azo-bis-isobutyl cyanide or 2,2'-Azobis(2,4-dimethylvaleronitrile).
The preparation method of a kind of lithium battery carbon the most according to claim 1 cladding lithium titanate anode material, it is characterised in that: described polymer monomer is any one in acrylic acid, methacrylic acid, acrylic acid methyl ester., methyl methacrylate, ethyl methacrylate, styrene.
The preparation method of a kind of lithium battery carbon the most according to claim 1 cladding lithium titanate anode material, it is characterised in that: described precipitant is any one in methanol, ethanol, petroleum ether.
A kind of lithium battery carbon the most according to claim 1 cladding lithium titanate anode material preparation method, it is characterised in that: described lithium-containing compound include one or several in lithium carbonate, Lithium hydrate, lithium oxalate, lithium acetate arbitrarily than mixture.
A kind of lithium battery carbon the most according to claim 1 cladding lithium titanate anode material preparation method, it is characterised in that: described titanium-containing oxide include one or several in rutile titanium dioxide, anatase titanium dioxide arbitrarily than mixture.
A kind of lithium battery carbon the most according to claim 1 cladding lithium titanate anode material preparation method, it is characterised in that: described noble gas include the one or two kinds of in helium, argon arbitrarily than mixture.
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| CN104505502B (en) * | 2014-12-26 | 2017-01-11 | 宁夏共享新能源材料有限公司 | Lithium titanate composite negative material for lithium ion battery and preparation method of lithium titanate composite negative material |
| CN104600280B (en) * | 2015-01-27 | 2017-02-22 | 中国东方电气集团有限公司 | Method for preparing carbon-coated lithium titanate |
| CN104733699B (en) * | 2015-03-20 | 2017-02-01 | 常州大学 | Method for preparing molybdenum dioxide coated lithium titanate negative electrode material |
| DE112018000205B4 (en) | 2017-02-21 | 2023-10-26 | International Advanced Research Centre For Powder Metallurgy And New Materials (Arci) | A METHOD FOR PRODUCING A HIGH PERFORMANCE LITHIUM TITANATE ANODE MATERIAL FOR LITHIUM-ION BATTERY APPLICATIONS |
| CN108336341A (en) * | 2018-02-28 | 2018-07-27 | 江苏金阳光新能源科技有限公司 | A kind of preparation method of high performance lithium ionic cell cathode material |
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| CN112290012A (en) * | 2020-10-20 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Preparation method of ternary cathode material of lithium ion battery |
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