CN114039032A - Titanium dioxide (B) negative electrode material with improved performance and preparation method thereof - Google Patents
Titanium dioxide (B) negative electrode material with improved performance and preparation method thereof Download PDFInfo
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- CN114039032A CN114039032A CN202111314247.7A CN202111314247A CN114039032A CN 114039032 A CN114039032 A CN 114039032A CN 202111314247 A CN202111314247 A CN 202111314247A CN 114039032 A CN114039032 A CN 114039032A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 54
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 34
- 239000002608 ionic liquid Substances 0.000 claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- 238000000227 grinding Methods 0.000 claims abstract description 28
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 25
- 239000010439 graphite Substances 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000002019 doping agent Substances 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 50
- 239000011268 mixed slurry Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 18
- -1 1-ethyl-3-methylimidazole tetrafluoroborate Chemical compound 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 238000001694 spray drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000005463 sulfonylimide group Chemical group 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 claims description 3
- PWVDAYXZBXAOSA-UHFFFAOYSA-N 2-butyl-1-methylpyrrolidine Chemical compound CCCCC1CCCN1C PWVDAYXZBXAOSA-UHFFFAOYSA-N 0.000 claims description 3
- GSBKRFGXEJLVMI-UHFFFAOYSA-N Nervonyl carnitine Chemical compound CCC[N+](C)(C)C GSBKRFGXEJLVMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- HPVKETCOXLFZKK-UHFFFAOYSA-N 2-butyl-1-methylpiperidine Chemical compound CCCCC1CCCCN1C HPVKETCOXLFZKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000002687 intercalation Effects 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 239000007770 graphite material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910010251 TiO2(B) Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 1
- OJHJIGKCTCVMDI-UHFFFAOYSA-N CCCCC1N(C)CCC1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O Chemical compound CCCCC1N(C)CCC1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O OJHJIGKCTCVMDI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a titanium dioxide (B) negative electrode material with improved performance and a preparation method thereof, wherein the titanium dioxide (B) negative electrode material is prepared from the following raw materials in parts by weight: 195 parts of titanium dioxide (B), 20-85 parts of ethyl orthosilicate, 60-135 parts of graphite, 90-130 parts of lithium source, 5-13 parts of dopant, 25-35 parts of carbon source and 35-45 parts of ionic liquid. The raw materials are prepared through the procedures of mixing, roasting, dispersing, grinding, drying, wrapping and sintering at one time; the cathode material prepared by the formula and the preparation method has excellent capacity performance, cycle performance, rate charge and discharge performance and first charge and discharge efficiency.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a titanium dioxide (B) negative electrode material with improved performance and a preparation method thereof.
Background
Titanium dioxide is an inorganic substance which is widely applied to industries such as paint, plastics, paper making, printing ink, chemical fiber, rubber, cosmetics and the like. Common titanium dioxide mainly comprises four crystalline phases: anatase phase, rutile phase, brookite phase and TiO2(B) And (4) phase(s). In all crystal phases, TiO2(B) The titanium dioxide belongs to a monoclinic system, has the most loose structure, has larger interlayer spacing and smaller density, is beneficial to the insertion and removal of lithium ions, and has potential superior performance when applied to the aspect of lithium ion batteries.
Meanwhile, most of the traditional lithium batteries adopt graphite materials as negative electrode materials, and because the graphite materials are high in graphitization degree and have a high layered structure, the lithium intercalation space is small, so that the lithium intercalation capacity of graphite is low, the cycle performance of graphite is poor, and the energy density of the batteries cannot be further greatly improved, therefore, the lithium intercalation capacity is high for TiO2(B) The technical problem in the field is to develop a preparation method of a titanium dioxide (B) cathode material which has good cycle performance and high first charge-discharge efficiency.
Disclosure of Invention
In view of the above, the present invention is directed to the defects of the prior art, and the main object of the present invention is to provide a titanium dioxide (B) negative electrode material with improved performance and a preparation method thereof, which has a larger lithium insertion capacity, and can improve the cycle performance and energy density of a battery compared to the conventional negative electrode material for a lithium battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a titanium dioxide (B) negative electrode material with improved performance comprises the following raw materials in parts by weight: 195 parts of titanium dioxide (B), 20-85 parts of ethyl orthosilicate, 60-135 parts of graphite, 90-130 parts of lithium source, 5-13 parts of dopant, 25-35 parts of carbon source and 35-45 parts of ionic liquid.
Preferably, the graphite is at least one of natural graphite and artificial graphite.
Preferably, the ionic liquid is one or more of N-methylbutylpyrrolidine bistrifluoromethylsulfonyl imide salt, N-methylbutylpiperidinbistrifluoromethylsulfonyl imide salt, 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt, 1-ethyl-3-methylimidazolium tetrafluoroborate, trimethylpropylammonium bistrifluoromethylsulfonyl imide salt and 1-hexyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt.
A preparation method of a titanium dioxide (B) negative electrode material with improved performance comprises the following steps:
(1) mixing: soaking titanium dioxide (B) in ethyl orthosilicate ethanol solvent, stirring and performing ultrasonic treatment for 0.5-2h to prepare a mixed solution;
(2) roasting: evaporating the mixed solution prepared in the step (1) to dryness in a water bath at the temperature of 60-90 ℃, drying the mixed solution in an oven, then placing the dried mixed solution in a muffle furnace, heating the mixed solution to 500-1000 ℃ at the speed of 3-8 ℃/min under the condition of oxygen enrichment, roasting the mixed solution at high temperature, and preserving the temperature for 2-5 hours to obtain surface modified titanium dioxide (B);
(3) dispersing: dispersing the surface-modified titanium dioxide (B), graphite, a lithium source, a doping agent and a carbon source in ethanol, and performing ultrasonic treatment for 1-4h to obtain mixed slurry;
(4) grinding: grinding the mixed slurry obtained in the step (3) for 1-5h by using a sand mill, wherein the grinding speed is 500-;
(5) and (3) drying: drying the ground mixed slurry into powder by using a spray dryer, wherein the air inlet temperature of the spray drying is 100-400 ℃, the air outlet temperature is 80-160 ℃, and the rotation rate of the constant flow pump is 50-150 r/min;
(6) and (3) wrapping: sequentially adding the material obtained in the step (5) and the ionic liquid into a high-speed stirrer, and dispersing for 1-6h at the rotation speed of 500-;
(7) and (3) sintering: and (4) placing the material obtained in the step (6) into an atmosphere protection furnace for sintering, raising the temperature to 500-1500 ℃ at the heating rate of 10-35 ℃/min, and preserving the temperature for 10-24 hours to obtain the cathode material.
As a preferable mode, the protective atmosphere used in the atmosphere protection furnace is selected from at least one of helium, nitrogen, argon and carbon dioxide.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and specifically, the technical scheme includes that:
according to the formula and the preparation method, the titanium dioxide (B) is selected as the core material, the structure of the titanium dioxide (B) is loose, the titanium dioxide (B) has larger interlayer spacing and smaller density, the lithium intercalation space is improved, the lithium intercalation capacity of the shell material is improved, the modified titanium dioxide (B) is mixed with graphite and then is combined through spray drying, the conductivity of the negative electrode material is improved, and the negative electrode material is wrapped and sintered with ionic liquid, so that the conductive polymer is further wrapped on the negative electrode material, the conductive polymer wrapping further improves the conductivity of the negative electrode material and inhibits the volume expansion and shrinkage of the negative electrode material in the charging and discharging processes, a stable SEI film is formed, the cycle performance of the battery is improved, and the energy density of the battery is improved.
To more clearly illustrate the features and effects of the present invention, the present invention is described in detail below with reference to specific examples.
Detailed Description
The invention discloses a titanium dioxide (B) negative electrode material with improved performance, which is prepared from the following raw materials in parts by weight: 195 parts of titanium dioxide (B), 20-85 parts of ethyl orthosilicate, 60-135 parts of graphite, 90-130 parts of lithium source, 5-13 parts of dopant, 25-35 parts of carbon source and 35-45 parts of ionic liquid; the graphite is at least one of natural graphite and artificial graphite; the ionic liquid is one or more than two of N-methylbutyl pyrrolidine bistrifluoromethyl sulfonyl imide salt, N-methylbutyl piperidine bistrifluoromethyl sulfonyl imide salt, 1-ethyl-3-methylimidazole tetrafluoroborate, trimethyl propyl ammonium bistrifluoromethyl sulfonyl imide salt and 1-hexyl-3-methylimidazole bistrifluoromethyl sulfonyl imide salt.
The invention also discloses a preparation method of the titanium dioxide (B) negative electrode material with improved performance, which comprises the following steps:
(1) mixing: soaking titanium dioxide (B) in ethyl orthosilicate ethanol solvent, stirring and performing ultrasonic treatment for 0.5-2h to obtain a mixed solution.
(2) Roasting: and (2) evaporating the mixed solution prepared in the step (1) to dryness in a water bath at the temperature of 60-90 ℃, drying the mixed solution in an oven, then placing the dried mixed solution in a muffle furnace, heating the mixed solution to the temperature of 500-1000 ℃ at the speed of 3-8 ℃/min under the condition of oxygen enrichment, roasting the mixed solution at high temperature, and preserving the temperature for 2-5 hours to obtain the surface modified titanium dioxide (B).
(3) Dispersing: dispersing the surface modified titanium dioxide (B), graphite, a lithium source, a doping agent and a carbon source in ethanol, and performing ultrasonic treatment for 1-4h to obtain mixed slurry.
(4) Grinding: grinding the mixed slurry obtained in the step (3) for 1-5h by using a sand mill, wherein the grinding speed is 500-.
(5) And (3) drying: and drying the ground mixed slurry into powder by using a spray dryer, wherein the air inlet temperature of the spray drying is 100-400 ℃, the air outlet temperature is 80-160 ℃, and the constant flow rotation rate is 50-150 r/min.
(6) And (3) wrapping: and (4) sequentially adding the material obtained in the step (5) and the ionic liquid into a high-speed stirrer, and dispersing for 1-6h at the rotation speed of 500-.
(7) And (3) sintering: and (3) placing the material obtained in the step (6) into an atmosphere protection furnace for sintering, wherein the protective atmosphere used in the atmosphere protection furnace is at least one of helium, nitrogen, argon and carbon dioxide, raising the temperature to 500-1500 ℃ at the heating rate of 10-35 ℃/min, and preserving the temperature for 10-24 hours to obtain the cathode material.
The present invention will be described in detail with reference to specific examples.
Example 1:
a titanium dioxide (B) negative electrode material with improved performance comprises the following raw materials in parts by weight: 130 parts of titanium dioxide (B), 20 parts of ethyl orthosilicate, 100 parts of graphite, 100 parts of lithium source, 5 parts of dopant, 28 parts of carbon source and 35 parts of ionic liquid; the ionic liquid is N-methylbutyl pyrrolidine bistrifluoromethane sulfimide salt and N-methylbutyl piperidine bistrifluoromethane sulfimide salt.
A preparation method of a titanium dioxide (B) negative electrode material with improved performance comprises the following steps:
(1) mixing: soaking titanium dioxide (B) in ethyl orthosilicate ethanol solvent, stirring and performing ultrasonic treatment for 2 hours to prepare a mixed solution.
(2) Roasting: and (2) evaporating the mixed solution prepared in the step (1) to dryness in a water bath at 80 ℃, drying the mixed solution in a drying oven, then placing the dried mixed solution in a muffle furnace, heating the mixed solution to 800 ℃ at the speed of 3 ℃/min under the condition of oxygen enrichment, roasting the mixed solution at high temperature, and keeping the temperature for 3 hours to obtain the surface modified titanium dioxide (B).
(3) Dispersing: dispersing the surface modified titanium dioxide (B), graphite, a lithium source, a doping agent and a carbon source in ethanol, and performing ultrasonic treatment for 1h to obtain mixed slurry.
(4) Grinding: and (4) grinding the mixed slurry obtained in the step (3) for 1 hour by using a sand mill, wherein the grinding speed is 2500 r/min.
(5) And (3) drying: and drying the ground mixed slurry into powder by using a spray dryer, wherein the air inlet temperature of the spray drying is 100 ℃, the air outlet temperature is 80 ℃, and the constant flow pump rotation speed is 100 r/min.
(6) And (3) wrapping: and (5) sequentially adding the material obtained in the step (5) and the ionic liquid into a high-speed stirrer, and dispersing for 1h at the rotating speed of 5000 r/min.
(7) And (3) sintering: and (4) placing the material obtained in the step (6) into an atmosphere protection furnace for sintering, wherein the protection atmosphere used in the atmosphere protection furnace is helium, heating to 500 ℃ at a heating rate of 10 ℃/min, and preserving heat for 24 hours to obtain the cathode material.
Example 2:
a titanium dioxide (B) negative electrode material with improved performance comprises the following raw materials in parts by weight: 155 parts of titanium dioxide (B), 40 parts of ethyl orthosilicate, 60 parts of graphite, 130 parts of lithium source, 7 parts of dopant, 35 parts of carbon source and 45 parts of ionic liquid; the ionic liquid is 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt and 1-ethyl-3-methylimidazole tetrafluoroborate.
A preparation method of a titanium dioxide (B) negative electrode material with improved performance comprises the following steps:
(1) mixing: soaking titanium dioxide (B) in ethyl orthosilicate ethanol solvent, stirring and performing ultrasonic treatment for 0.5h to obtain a mixed solution.
(2) Roasting: and (2) evaporating the mixed solution prepared in the step (1) to dryness in a water bath at 60 ℃, drying the mixed solution in a drying oven, then placing the dried mixed solution in a muffle furnace, heating the mixed solution to 1000 ℃ at the speed of 8 ℃/min under the condition of oxygen enrichment, roasting the mixed solution at high temperature, and keeping the temperature for 2 hours to obtain the surface modified titanium dioxide (B).
(3) Dispersing: dispersing the surface modified titanium dioxide (B), graphite, a lithium source, a doping agent and a carbon source in ethanol, and performing ultrasonic treatment for 3 hours to obtain mixed slurry.
(4) Grinding: and (4) grinding the mixed slurry obtained in the step (3) for 5 hours by using a sand mill, wherein the grinding speed is 500 r/min.
(5) And (3) drying: and drying the ground mixed slurry into powder by using a spray dryer, wherein the air inlet temperature of the spray drying is 400 ℃, the air outlet temperature is 160 ℃, and the constant flow pump rotation speed is 500 r/min.
(6) And (3) wrapping: and (5) sequentially adding the material obtained in the step (5) and the ionic liquid into a high-speed stirrer, and dispersing for 6 hours at a rotating speed of 50 r/min.
(7) And (3) sintering: and (4) placing the material obtained in the step (6) into an atmosphere protection furnace for sintering, wherein the protection atmosphere used in the atmosphere protection furnace is nitrogen, heating to 1500 ℃ at the heating rate of 35 ℃/min, and preserving heat for 10 hours to obtain the cathode material.
Example 3:
a titanium dioxide (B) negative electrode material with improved performance comprises the following raw materials in parts by weight: 195 parts of titanium dioxide (B), 40 parts of ethyl orthosilicate, 135 parts of graphite, 90 parts of lithium source, 13 parts of dopant, 35 parts of carbon source and 45 parts of ionic liquid; the ionic liquid is 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt and 1-ethyl-3-methylimidazole tetrafluoroborate.
A preparation method of a titanium dioxide (B) negative electrode material with improved performance comprises the following steps:
(1) mixing: soaking titanium dioxide (B) in ethyl orthosilicate ethanol solvent, stirring and performing ultrasonic treatment for 1.5h to obtain a mixed solution.
(2) Roasting: and (2) evaporating the mixed solution prepared in the step (1) to dryness in a water bath at 90 ℃, drying the mixed solution in a drying oven, then placing the dried mixed solution in a muffle furnace, heating the mixed solution to 500 ℃ at the speed of 5 ℃/min under the condition of oxygen enrichment, roasting the mixed solution at high temperature, and keeping the temperature for 5 hours to obtain the surface modified titanium dioxide (B).
(3) Dispersing: dispersing the surface modified titanium dioxide (B), graphite, a lithium source, a doping agent and a carbon source in ethanol, and performing ultrasonic treatment for 4 hours to obtain mixed slurry.
(4) Grinding: and (4) grinding the mixed slurry obtained in the step (3) for 3 hours by using a sand mill, wherein the grinding speed is 1500 r/min.
(5) And (3) drying: and drying the ground mixed slurry into powder by using a spray dryer, wherein the air inlet temperature of the spray drying is 200 ℃, the air outlet temperature is 120 ℃, and the constant flow pump rotation speed is 150 r/min.
(6) And (3) wrapping: and (4) sequentially adding the material obtained in the step (5) and the ionic liquid into a high-speed stirrer, and dispersing for 5 hours at a rotating speed of 500 r/min.
(7) And (3) sintering: and (4) placing the material obtained in the step (6) into an atmosphere protection furnace for sintering, wherein the protection atmosphere used in the atmosphere protection furnace is nitrogen, raising the temperature to 1200 ℃ at the heating rate of 20 ℃/min, and preserving the temperature for 16 hours to obtain the cathode material.
Example 4:
a titanium dioxide (B) negative electrode material with improved performance comprises the following raw materials in parts by weight: 155 parts of titanium dioxide (B), 85 parts of ethyl orthosilicate, 115 parts of graphite, 90 parts of lithium source, 10 parts of dopant, 25 parts of carbon source and 40 parts of ionic liquid; the ionic liquid is trimethyl propyl ammonium bis (trifluoromethanesulfonimide) salt and 1-hexyl-3-methylimidazole bis (trifluoromethanesulfonimide) salt.
A preparation method of a titanium dioxide (B) negative electrode material with improved performance comprises the following steps:
(1) mixing: soaking titanium dioxide (B) in ethyl orthosilicate ethanol solvent, stirring and performing ultrasonic treatment for 1h to prepare a mixed solution.
(2) Roasting: and (2) evaporating the mixed solution prepared in the step (1) to dryness in a water bath at 75 ℃, drying the mixed solution in a drying oven, then placing the dried mixed solution in a muffle furnace, heating the mixed solution to 600 ℃ at the speed of 6 ℃/min under the condition of oxygen enrichment, roasting the mixed solution at high temperature, and keeping the temperature for 3 hours to obtain the surface modified titanium dioxide (B).
(3) Dispersing: dispersing the surface modified titanium dioxide (B), graphite, a lithium source, a doping agent and a carbon source in ethanol, and performing ultrasonic treatment for 2.5 hours to obtain mixed slurry.
(4) Grinding: and (4) grinding the mixed slurry obtained in the step (3) for 3.5 hours by using a sand mill, wherein the grinding speed is 900 r/min.
(5) And (3) drying: and drying the ground mixed slurry into powder by using a spray dryer, wherein the air inlet temperature of the spray drying is 300 ℃, the air outlet temperature is 120 ℃, and the constant flow pump rotation speed is 150 r/min.
(6) And (3) wrapping: and (4) sequentially adding the material obtained in the step (5) and the ionic liquid into a high-speed stirrer, and dispersing for 4 hours at a rotating speed of 3000 r/min.
(7) And (3) sintering: and (4) placing the material obtained in the step (6) into an atmosphere protection furnace for sintering, wherein the protection atmosphere used in the atmosphere protection furnace is argon and carbon dioxide, raising the temperature to 1150 ℃ at a heating rate of 20 ℃/min, and preserving the temperature for 18 hours to obtain the cathode material.
Example 5:
a titanium dioxide (B) negative electrode material with improved performance comprises the following raw materials in parts by weight: 180 parts of titanium dioxide (B), 55 parts of ethyl orthosilicate, 125 parts of graphite, 115 parts of lithium source, 10 parts of dopant, 25 parts of carbon source and 40 parts of ionic liquid; the ionic liquid is 1-hexyl-3-methylimidazole bistrifluoromethanesulfonylimide salt.
A preparation method of a titanium dioxide (B) negative electrode material with improved performance comprises the following steps:
(1) mixing: soaking titanium dioxide (B) in ethyl orthosilicate ethanol solvent, stirring and performing ultrasonic treatment for 1h to prepare a mixed solution.
(2) Roasting: and (2) evaporating the mixed solution prepared in the step (1) to dryness in a water bath at 75 ℃, drying the mixed solution in a drying oven, then placing the dried mixed solution in a muffle furnace, heating the mixed solution to 600 ℃ at the speed of 6 ℃/min under the condition of oxygen enrichment, roasting the mixed solution at high temperature, and keeping the temperature for 3 hours to obtain the surface modified titanium dioxide (B).
(3) Dispersing: dispersing the surface modified titanium dioxide (B), graphite, a lithium source, a doping agent and a carbon source in ethanol, and performing ultrasonic treatment for 3 hours to obtain mixed slurry.
(4) Grinding: and (4) grinding the mixed slurry obtained in the step (3) for 3 hours by using a sand mill, wherein the grinding speed is 1200 r/min.
(5) And (3) drying: and drying the ground mixed slurry into powder by using a spray dryer, wherein the air inlet temperature of the spray drying is 300 ℃, the air outlet temperature is 160 ℃, and the constant flow pump rotation speed is 150 r/min.
(6) And (3) wrapping: and (4) sequentially adding the material obtained in the step (5) and the ionic liquid into a high-speed stirrer, and dispersing for 4 hours at a rotating speed of 3000 r/min.
(7) And (3) sintering: and (4) placing the material obtained in the step (6) into an atmosphere protection furnace for sintering, wherein the protection atmosphere used in the atmosphere protection furnace is carbon dioxide, heating to 1050 ℃ at the heating rate of 20 ℃/min, and preserving heat for 20 hours to obtain the cathode material.
Example 6:
a titanium dioxide (B) negative electrode material with improved performance comprises the following raw materials in parts by weight: 155 parts of titanium dioxide (B), 35 parts of ethyl orthosilicate, 85 parts of graphite, 120 parts of lithium source, 12 parts of dopant, 28 parts of carbon source and 37 parts of ionic liquid; the ionic liquid is N-methylbutyl pyrrolidine bistrifluoromethanesulfonimide salt.
A preparation method of a titanium dioxide (B) negative electrode material with improved performance comprises the following steps:
(1) mixing: soaking titanium dioxide (B) in ethyl orthosilicate ethanol solvent, stirring and performing ultrasonic treatment for 2 hours to prepare a mixed solution.
(2) Roasting: and (2) evaporating the mixed solution prepared in the step (1) to dryness in a water bath at 85 ℃, drying in a drying oven, then placing in a muffle furnace, heating to 900 ℃ at the speed of 7 ℃/min under the condition of oxygen enrichment, roasting at high temperature, and preserving heat for 3h to obtain the surface modified titanium dioxide (B).
(3) Dispersing: dispersing the surface modified titanium dioxide (B), graphite, a lithium source, a doping agent and a carbon source in ethanol, and performing ultrasonic treatment for 1.5h to obtain mixed slurry.
(4) Grinding: and (4) grinding the mixed slurry obtained in the step (3) for 1.5h by using a sand mill, wherein the grinding speed is 2250 r/min.
(5) And (3) drying: and drying the ground mixed slurry into powder by using a spray dryer, wherein the air inlet temperature of the spray drying is 350 ℃, the air outlet temperature is 150 ℃, and the constant flow pump rotation speed is 120 r/min.
(6) And (3) wrapping: and (5) sequentially adding the material obtained in the step (5) and the ionic liquid into a high-speed stirrer, and dispersing for 4 hours at the rotating speed of 3600 r/min.
(7) And (3) sintering: and (4) placing the material obtained in the step (6) into an atmosphere protection furnace for sintering, wherein the protection atmosphere used in the atmosphere protection furnace is carbon dioxide, heating to 1050 ℃ at the heating rate of 25 ℃/min, and preserving heat for 20 hours to obtain the cathode material.
Comparative example 1: a general artificial graphite material obtained using polycarbonate as a covering material.
Comparative example 2: a general artificial graphite material obtained using pitch as a coating material.
And (3) electrochemical performance testing:
in order to test the performance of the lithium ion battery cathode material of the ionic liquid coated titanium dioxide (B) cathode material, a half-cell test method is used for testing, the cathode material of the above embodiment and comparative example, SBR (solid content is 50 percent), CMC and Super-p are 95.5: 2: 1.5: 1 (weight ratio), a proper amount of deionized water is added to be blended into slurry, the slurry is coated on a copper foil and dried in a vacuum drying oven for 12 hours to prepare a cathode piece, and the electrolyte is 1M LiPF6And the/EC + DEC + DMC is 1: 1, the polypropylene microporous membrane is a diaphragm, the counter electrode is a lithium sheet, and the battery is assembled. A constant-current charge and discharge experiment is carried out in a LAND battery test system, the charge and discharge voltage is limited to 0.01-3.0V, data collection and control are carried out by a charge and discharge cabinet controlled by a computer, and the obtained data are shown in the following table 1.
As can be seen from Table 1, the prepared negative electrode material has excellent capacity performance, cycle performance, rate charge and discharge performance and first charge and discharge efficiency.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (5)
1. A titanium dioxide (B) negative electrode material with improved performance is characterized in that: the feed is prepared from the following raw materials in parts by weight: 195 parts of titanium dioxide (B), 20-85 parts of ethyl orthosilicate, 60-135 parts of graphite, 90-130 parts of lithium source, 5-13 parts of dopant, 25-35 parts of carbon source and 35-45 parts of ionic liquid.
2. The titanium dioxide (B) negative electrode material with improved performance as claimed in claim 1, wherein: the graphite is at least one of natural graphite and artificial graphite.
3. The titanium dioxide (B) negative electrode material with improved performance as claimed in claim 1, wherein: the ionic liquid is one or more than two of N-methylbutyl pyrrolidine bistrifluoromethyl sulfonyl imide salt, N-methylbutyl piperidine bistrifluoromethyl sulfonyl imide salt, 1-ethyl-3-methylimidazole tetrafluoroborate, trimethyl propyl ammonium bistrifluoromethyl sulfonyl imide salt and 1-hexyl-3-methylimidazole bistrifluoromethyl sulfonyl imide salt.
4. A method for producing a titanium dioxide (B) negative electrode material with improved properties as claimed in any one of claims 1 to 3, wherein: the method comprises the following steps:
(1) mixing: soaking titanium dioxide (B) in ethyl orthosilicate ethanol solvent, stirring and performing ultrasonic treatment for 0.5-2h to prepare a mixed solution;
(2) roasting: evaporating the mixed solution prepared in the step (1) to dryness in a water bath at the temperature of 60-90 ℃, drying the mixed solution in an oven, then placing the dried mixed solution in a muffle furnace, heating the mixed solution to 500-1000 ℃ at the speed of 3-8 ℃/min under the condition of oxygen enrichment, roasting the mixed solution at high temperature, and preserving the temperature for 2-5 hours to obtain surface modified titanium dioxide (B);
(3) dispersing: dispersing the surface-modified titanium dioxide (B), graphite, a lithium source, a doping agent and a carbon source in ethanol, and performing ultrasonic treatment for 1-4h to obtain mixed slurry;
(4) grinding: grinding the mixed slurry obtained in the step (3) for 1-5h by using a sand mill, wherein the grinding speed is 500-;
(5) and (3) drying: drying the ground mixed slurry into powder by using a spray dryer, wherein the air inlet temperature of the spray drying is 100-400 ℃, the air outlet temperature is 80-160 ℃, and the rotation rate of the constant flow pump is 50-150 r/min;
(6) and (3) wrapping: sequentially adding the material obtained in the step (5) and the ionic liquid into a high-speed stirrer, and dispersing for 1-6h at the rotation speed of 500-;
(7) and (3) sintering: and (4) placing the material obtained in the step (6) into an atmosphere protection furnace for sintering, raising the temperature to 500-1500 ℃ at the heating rate of 10-35 ℃/min, and preserving the temperature for 10-24 hours to obtain the cathode material.
5. The method for preparing the titanium dioxide (B) negative electrode material with improved performance as claimed in claim 4, wherein: the protective atmosphere used in the atmosphere protective furnace is selected from at least one of helium, nitrogen, argon and carbon dioxide.
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