CN107117648A - A kind of preparation method of lithium ion battery negative material - Google Patents
A kind of preparation method of lithium ion battery negative material Download PDFInfo
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- CN107117648A CN107117648A CN201710266435.4A CN201710266435A CN107117648A CN 107117648 A CN107117648 A CN 107117648A CN 201710266435 A CN201710266435 A CN 201710266435A CN 107117648 A CN107117648 A CN 107117648A
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- ion battery
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 150000003608 titanium Chemical class 0.000 claims abstract description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- QJKSCTQFTLWJLX-UHFFFAOYSA-N C(C1=CC=C(C(=O)O)C=C1)(=O)O.NNC(NN)=O Chemical compound C(C1=CC=C(C(=O)O)C=C1)(=O)O.NNC(NN)=O QJKSCTQFTLWJLX-UHFFFAOYSA-N 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 9
- 239000010406 cathode material Substances 0.000 abstract description 2
- 229910009866 Ti5O12 Inorganic materials 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 238000001354 calcination Methods 0.000 description 18
- 238000000227 grinding Methods 0.000 description 18
- 239000010936 titanium Substances 0.000 description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 238000013019 agitation Methods 0.000 description 9
- 239000003814 drug Substances 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910011956 Li4Ti5 Inorganic materials 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of preparation method of lithium ion battery negative material, belongs to new energy lithium cell cathode material technical field.The method of the invention is：Template, organic solvent, part and organic titanium salt are well mixed, then above solution is transferred in autoclave again, with solvent-thermal method, at high temperature under high pressure with organic solvent, organic titanium salt and part are self-assembled into as metal-organic framework materials in the presence of template（MOFs）, then be put into after resulting product is well mixed according to a certain percentage with lithium source in resistance furnace and calcined with certain condition, that is, obtain negative pole pole material（Li4Ti5O12）.The Li that the method for the invention is prepared4Ti5O12It is a kind of minimum " zero strain " material of strain, allows battery under extreme high/low temperature condition and Volume Changes are all minimum during inside battery reaction, so also just impart this negative material outstanding high temperature performance and cycle performance.
Description
Technical field
The present invention relates to being a kind of preparation method of lithium ion battery negative material, belong to new energy lithium cell cathode material
Technical field.
Background technology
In the last few years, lithium ion battery had that power characteristic is good, cheap due to it, had extended cycle life and the Zhuo such as safety and stability
More performance, so the development of lithium ion battery has been subjected to the great attention of each side.Negative material is played in lithium ion battery
Very important effect spinel type lithium titanate (Li4Ti5012) as lithium ion battery negative material there is obvious advantage：It is
A kind of unstressed insertion material, hardly recurring structure changes in charge and discharge process, good cycle；There is good discharge and recharge
Platform；Do not reacted with electrolyte；It is cheap, easily is prepared compared with the carbon negative pole material of commercialization, and generally there is more preferably electricity
Chemical property and security；Compared with alloy type negative material, it is easier to prepare, cost is lower.Current people are to spinel-type
Lithium titanate (Li4Ti5012) negative material done substantial amounts of research work, but the material still suffer from can not realize high conductivity with
The problem of high-tap density is mutually unified.This structure and preparation method with material is closely related, in Li4Ti5012Negative material
In preparation technology, presently mainly traditional solid reaction process and sol-gel method, these methods can prepare nanometer
Li4Ti5012Particle, by reducing Li+Diffusion path improves electric conductivity；But do not have on the problem of solving bulk density
To much effects.
The content of the invention
It is an object of the invention to provide a kind of preparation method of lithium ion battery negative material, following step is specifically included
Suddenly：
（1）At room temperature, it is 1 according to mol ratio by organic titanium salt, part, template and organic solvent:(1.5~3):(15~
30)：(40 ~ 60) mixed solution is obtained after being well mixed.
（2）By step（1）Obtained mixed solution is transferred in autoclave, at 120 ~ 200 DEG C react 12~
36h。
（3）Will（2）Reaction obtains turbid liquid and carries out suction filtration, is ground after vacuum drying, 300 mesh sieves is crossed, then by powder
2~12 hours are being calcined at a temperature of 200~580 DEG C, that is, are obtaining porous titanium dioxide.
（4）Will（3）It is (0.8~1.25) in molar ratio with lithium source to obtain porous titanium dioxide:1 is sufficiently mixed uniformly,
2~20 hours are calcined at a temperature of 650~950 DEG C, that is, obtain lithium ion battery negative material Li4Ti5O12。
It is preferred that, step of the present invention（1）Described in template be methanol（CH3OH）, formic acid（HCOOH）Or P123（Polycyclic
Oxidative ethane-PPOX-PEO triblock copolymer C5H10O2）.
It is preferred that, step of the present invention（1）Described in organic solvent be dimethylformamide（C3H7NO）.
It is preferred that, step of the present invention（1）Described in part be terephthalic acid (TPA)（HOOCC6H4COOH）Or diaminourea is to benzene
Dioctyl phthalate（C8H7NO4）.
It is preferred that, step of the present invention（1）Described in organic titanium salt be tetrabutyl titanate（C16H36O4Ti）, butyl titanate
（C16H36O4Ti）, butyl titanate（C16H36O4Ti）, isopropyl titanate（C12H28O4Ti）, isopropyl titanate（Ti4(OCH3)16）Or
Titanium tetraisopropylate（C12H28O4Ti）.
It is preferred that, step of the present invention（4）Described in lithium source be lithium carbonate, lithium hydroxide, lithium acetate or lithium nitrate.
The advantages of the present invention are：
Lithium titanate Li prepared by the method for the invention4Ti5012Negative material, lithium source is easier to be attached to poriferous titanium dioxide surface
On, it is possible to reduce the volatilization in sintering process, it is easier to prepare the lithium titanate Li for meeting stoichiometric proportion4Ti5012Negative pole
Material；Simultaneously porous structure adds lithium titanate Li4Ti5012Negative material with the contact area of electrolyte, accelerate lithium from
Deintercalation of the son in battery charge and discharge process and enter embedding, ionic conductivity is added, so as to optimize the electrochemistry of electrode material
Performance.
Brief description of the drawings
Fig. 1 is the XRD for the MOFs (MIL-125@Ti) that the embodiment of the present invention 1 is synthesized；
Fig. 2 is the TiO obtained after the MOFs (MIL-125@Ti) that the embodiment of the present invention 1 is synthesized is sintered2XRD；
Fig. 3 is the TiO obtained after the MOFs (MIL-125@Ti) that the embodiment of the present invention 1 is synthesized is sintered2BET figure；
Fig. 4 is lithium titanate anode material first charge-discharge figure prepared by the embodiment of the present invention 1.
Embodiment
The present invention is further illustrated with reference to specific embodiment, it should be pointed out that following examples are served only for
Bright specific implementation method of the invention, can not limit rights protection scope of the present invention.
Embodiment 1
The synthetic method of lithium ion battery negative material described in the present embodiment, specifically includes following steps：
（1）At room temperature, it is 1: 2: 15: 60 according to mol ratio by butyl titanate, terephthalic acid (TPA), methanol and dimethylformamide
Mixed solution, and mechanical agitation and ultrasonic vibration sufficiently long time are made into, medicine therein is well mixed.
（2）Will（1）In be well mixed solution be transferred to the high pressure that temperature has been raised to 150 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 12 hours, reaction obtains MOFs（MIL-125@Ti）.
（3）Will（2）Reaction obtains turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 degrees Celsius, is dried in vacuo whole
At night, finally desciccate is ground using agate mortar, until crossing the sieve of 300 mesh.
（4）Will（3）The middle powder by grinding, in atmosphere with 380 DEG C of 4 hours of calcining, that is, obtains porous silica
Titanium（TiO2）.
（5）Will（4）The middle TiO by grinding2Powder is sufficiently mixed uniformly, in air for 1.25: 1 in molar ratio with lithium source
In with 850 DEG C calcining 20 hours, that is, obtain negative material（Li4Ti5O12）.
XRD picture such as Fig. 1 of MOFs (MIL-125@Ti) obtained by the present embodiment step (2), it can be seen that synthesized
Product really be porous metal-organic framework materials；By Fig. 2, i.e. the present embodiment step (4) synthesis porous TiO2XRD
Figure, it can be seen that the TiO obtained by under this sintering temperature2For Anatase；Synthesized by Fig. 3, i.e. the present embodiment step (4)
Porous TiO2BET figure, final result show titanium dioxide specific surface area be 296.614 m2g-1；As seen from Figure 4
Prepared negative material first discharge specific capacity is 160.4mAhg-1, 50 capability retentions of circulation are under 1C multiplying power
95.69%.
Embodiment 2
（1）At room temperature, it is 1 according to mol ratio by tetrabutyl titanate, formic acid, diaminourea terephthalic acid (TPA) and dimethylformamide
: be made into mixed solution, and mechanical agitation and ultrasonic vibration sufficiently long time at 1.5: 20: 60, is well mixed medicine therein.
（2）Will（1）In be well mixed solution be transferred to the high pressure that temperature has been raised to 120 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 24 hours, reaction obtains MOFs（MIL-125-NH2@Ti）.
（3）Will（2）Reaction obtains turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 degrees Celsius, is dried in vacuo whole
At night, finally desciccate is ground using agate mortar, until crossing the sieve of 300 mesh.
（4）Will（3）The middle powder by grinding, in atmosphere with 480 DEG C of 2 hours of calcining, that is, obtains porous silica
Titanium（TiO2）.
（5）Will（4）The middle TiO by grinding2Powder is sufficiently mixed uniformly, in atmosphere for 1: 1 in molar ratio with lithium source
With 950 DEG C of 14 hours of calcining, that is, obtain negative material（Li4Ti5O12）.
Negative material first discharge specific capacity prepared by the present embodiment is 164.8mAhg-1, 50 are circulated under 1C multiplying power
Secondary capability retention is 96.42%.
Embodiment 3
（1）At room temperature, it is 1: 1.5 according to mol ratio by isopropyl titanate, methanol, terephthalic acid (TPA) and dimethylformamide:
Be made into mixed solution, and mechanical agitation and ultrasonic vibration sufficiently long time at 25: 60, is well mixed medicine therein.
（2）Will（1）In be well mixed solution be transferred to the high pressure that temperature has been raised to 120 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 36 hours, reaction obtains MOFs（MIL-125@Ti）.
（3）Will（2）Reaction obtains turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 degrees Celsius, is dried in vacuo whole
At night, finally desciccate is ground using agate mortar, until crossing the sieve of 300 mesh.
（4）Will（3）The middle powder by grinding, in atmosphere with 580 DEG C of 2 hours of calcining, that is, obtains porous silica
Titanium（TiO2）.
（5）Will（4）The middle TiO by grinding2Powder is sufficiently mixed uniformly, in air for 0.8: 1 in molar ratio with lithium source
In with 650 DEG C calcining 20 hours, that is, obtain negative material（Li4Ti5O12）.
Negative material first discharge specific capacity prepared by the present embodiment is 158.9mAhg-1, 50 are circulated under 1C multiplying power
Secondary capability retention is 93.63%.
Embodiment 4
（1）At room temperature, it is 1 according to mol ratio by butyl titanate, formic acid, diaminourea terephthalic acid (TPA) and dimethylformamide
: be made into mixed solution, and mechanical agitation and ultrasonic vibration sufficiently long time at 2.5: 30: 60, is well mixed medicine therein.
（2）Will（1）In be well mixed solution be transferred to the high pressure that temperature has been raised to 200 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 18 hours, reaction obtains MOFs（MIL-125-NH2@Ti）.
（3）Will（2）Reaction obtains turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 degrees Celsius, is dried in vacuo whole
At night, finally desciccate is ground using agate mortar, until crossing the sieve of 300 mesh.
（4）Will（3）The middle powder by grinding, in atmosphere with 580 DEG C of 6 hours of calcining, that is, obtains porous silica
Titanium（TiO2）.
（5）Will（4）The middle TiO by grinding2Powder is sufficiently mixed uniformly, in air for 0.8: 1 in molar ratio with lithium source
In with 800 calcining 20 hours, that is, obtain negative material（Li4Ti5O12）.
Negative material first discharge specific capacity prepared by the present embodiment is 163.6mAhg-1, 50 are circulated under 1C multiplying power
Secondary capability retention is 94.87%.
Embodiment 5
（1）At room temperature, it is 1: 3: 15: 50 according to mol ratio by butyl titanate, methanol, terephthalic acid (TPA) and dimethylformamide
Mixed solution, and mechanical agitation and ultrasonic vibration sufficiently long time are made into, medicine therein is well mixed.
（2）Will（1）In be well mixed solution be transferred to the high pressure that temperature has been raised to 180 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 12 hours, reaction obtains MOFs（MIL-125@Ti）.
（3）Will（2）Reaction obtains turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 degrees Celsius, is dried in vacuo whole
At night, finally desciccate is ground using agate mortar, until crossing the sieve of 300 mesh.
（4）Will（3）The middle powder by grinding, in atmosphere with 200 DEG C of 12 hours of calcining, that is, obtains porous silica
Titanium（TiO2）.
（5）Will（4）The middle TiO by grinding2Powder is sufficiently mixed uniformly, in air for 1.1: 1 in molar ratio with lithium source
In with 700 DEG C calcining 10 hours, that is, obtain negative material（Li4Ti5O12）.
Negative material first discharge specific capacity prepared by the present embodiment is 155.7mAhg-1, 50 are circulated under 1C multiplying power
Secondary capability retention is 97.2%.
Embodiment 6
（1）At room temperature, it is 1 according to mol ratio by tetrabutyl titanate, formic acid, diaminourea terephthalic acid (TPA) and dimethylformamide
: be made into mixed solution, and mechanical agitation and ultrasonic vibration sufficiently long time at 1.5: 15: 40, is well mixed medicine therein.
（2）Will（1）In be well mixed solution be transferred to the high pressure that temperature has been raised to 150 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 30 hours, reaction obtains MOFs（MIL-125-NH2@Ti）.
（3）Will（2）Reaction obtains turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 degrees Celsius, is dried in vacuo whole
At night, finally desciccate is ground using agate mortar, until crossing the sieve of 300 mesh.
（4）Will（3）The middle powder by grinding, in atmosphere with 580 DEG C of 6 hours of calcining, that is, obtains finally coating
Positive electrode.Obtain poriferous titanium dioxide（TiO2）.
（5）Will（4）The middle TiO by grinding2Powder is sufficiently mixed uniformly, in air for 0.9: 1 in molar ratio with lithium source
In with 900 DEG C calcining 15 hours, that is, obtain negative material（Li4Ti5O12）.
Negative material first discharge specific capacity prepared by the present embodiment is 158.4mAhg-1, 50 are circulated under 1C multiplying power
Secondary capability retention is 98.45%.
Embodiment 7
（1）At room temperature, it is 1: 1.5 according to mol ratio by isopropyl titanate, methanol, terephthalic acid (TPA) and dimethylformamide:
Be made into mixed solution, and mechanical agitation and ultrasonic vibration sufficiently long time at 20: 60, is well mixed medicine therein.
（2）Will（1）In be well mixed solution be transferred to the high pressure that temperature has been raised to 180 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 12 hours, reaction obtains MOFs（MIL-125@Ti）.
（3）Will（2）Reaction obtains turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 degrees Celsius, is dried in vacuo whole
At night, finally desciccate is ground using agate mortar, until crossing the sieve of 300 mesh.
（4）Will（3）The middle powder by grinding, in atmosphere with 380 DEG C of 8 hours of calcining, that is, obtains porous silica
Titanium（TiO2）.
（5）Will（4）The middle TiO by grinding2Powder is sufficiently mixed uniformly, in air for 0.8: 1 in molar ratio with lithium source
In with 650 calcining 10 hours, that is, obtain negative material（Li4Ti5O12）.
Negative material first discharge specific capacity prepared by the present embodiment is 163.1mAhg-1, 50 are circulated under 1C multiplying power
Secondary capability retention is 92.88%.
Embodiment 8
（1）At room temperature, it is 1 according to mol ratio by butyl titanate, formic acid, diaminourea terephthalic acid (TPA) and dimethylformamide
: be made into mixed solution, and mechanical agitation and ultrasonic vibration sufficiently long time at 2.5: 25: 60, is well mixed medicine therein.
（2）Will（1）In be well mixed solution be transferred to the high pressure that temperature has been raised to 120 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 36 hours, reaction obtains initial positive electrode LiNi0.5Co0.2Mn0.3O2And MOFs（MIL-
125-NH2@Ti）Mixture.
（3）Will（2）Reaction obtains turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 degrees Celsius, is dried in vacuo whole
At night, finally desciccate is ground using agate mortar, until crossing the sieve of 300 mesh.
（4）Will（3）The middle powder by grinding, in atmosphere with 580 DEG C of 10 hours of calcining, that is, obtains porous dioxy
Change titanium（TiO2）.
（5）Will（4）The middle TiO by grinding2Powder is sufficiently mixed uniformly, in air for 1.25: 1 in molar ratio with lithium source
In with 950 DEG C calcining 6 hours, that is, obtain negative material（Li4Ti5O12）.
Negative material first discharge specific capacity prepared by the present embodiment is 151.5mAhg-1, 50 are circulated under 1C multiplying power
Secondary capability retention is 96.73%.
Embodiment 9
（1）At room temperature, it is 1: 2.5: 30 according to mol ratio by isopropyl titanate, methanol, terephthalic acid (TPA) and dimethylformamide:
60 are made into mixed solution, and mechanical agitation and ultrasonic vibration sufficiently long time, are well mixed medicine therein.
（2）Will（1）In be well mixed solution be transferred to the high pressure that temperature has been raised to 200 DEG C of polytetrafluoroethyllining lining
In reactor, and kept for 36 hours, reaction obtains MOFs（MIL-125@Ti）.
（3）Will（2）Reaction obtains turbid liquid and carries out suction filtration, then by obtained filter cake more than 80 degrees Celsius, is dried in vacuo whole
At night, finally desciccate is ground using agate mortar, until crossing the sieve of 300 mesh.
（4）Will（3）The middle powder by grinding, in atmosphere with 380 DEG C of 12 hours of calcining, that is, obtains porous dioxy
Change titanium（TiO2）.
（5）Will（4）The middle TiO by grinding2Powder is sufficiently mixed uniformly, in atmosphere for 1: 1 in molar ratio with lithium source
With 850 DEG C of 6 hours of calcining, that is, obtain negative material（Li4Ti5O12）.
Negative material first discharge specific capacity prepared by the present embodiment is 156.6mAhg-1, 50 are circulated under 1C multiplying power
Secondary capability retention is 94.93%.
Claims (6)
1. a kind of preparation method of lithium ion battery negative material, it is characterised in that specifically include following steps：
（1）At room temperature, it is 1 according to mol ratio by organic titanium salt, part, template and organic solvent:(1.5~3):(15~
30)：(40 ~ 60) mixed solution is obtained after being well mixed；
（2）By step（1）Obtained mixed solution is transferred in autoclave, and 12~36h is reacted at 120 ~ 200 DEG C；
（3）Will（2）Reaction obtains turbid liquid and carries out suction filtration, is ground after vacuum drying, crosses 300 mesh sieves, then by powder
2~12 hours are calcined at a temperature of 200~580 DEG C, that is, obtain porous titanium dioxide；
（4）Will（3）It is (0.8~1.25) in molar ratio with lithium source to obtain porous titanium dioxide:1 is sufficiently mixed uniformly, 650
2~20 hours are calcined at a temperature of~950 DEG C, that is, obtain lithium ion battery negative material Li4Ti5O12。
2. according to the preparation method of claim 1 lithium ion battery negative material, it is characterised in that：Step（1）Described in template
Agent is methanol, formic acid or P123。
3. according to the preparation method of claim 1 lithium ion battery negative material, it is characterised in that：Step（1）Described in it is organic
Solvent is dimethylformamide.
4. according to the preparation method of claim 1 lithium ion battery negative material, it is characterised in that：Step（1）Described in part
For terephthalic acid (TPA) or diaminourea terephthalic acid (TPA).
5. according to the preparation method of claim 1 lithium ion battery negative material, it is characterised in that：Step（1）Described in it is organic
Titanium salt is tetrabutyl titanate, butyl titanate, butyl titanate, isopropyl titanate, isopropyl titanate or titanium tetraisopropylate.
6. according to the preparation method of claim 1 lithium ion battery negative material, it is characterised in that：Step（4）Described in lithium
Source is lithium carbonate, lithium hydroxide, lithium acetate or lithium nitrate.
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| CN109880114A (en) * | 2019-03-12 | 2019-06-14 | 北京科技大学 | A kind of Ti-MOFs material and preparation method thereof using solvent structure |
| CN110165196A (en) * | 2019-06-13 | 2019-08-23 | 吉林大学 | A kind of NCM333With ZIF-8 composite positive pole and preparation method |
| CN110982083A (en) * | 2019-12-05 | 2020-04-10 | 浙江华恒复合材料有限公司 | Microporous metal organic framework material used as getter of vacuum insulation board and synthetic method thereof |
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| CN114784261A (en) * | 2022-06-21 | 2022-07-22 | 宜宾锂宝新材料有限公司 | Lithium battery positive electrode material and preparation method thereof |
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| CN108777290A (en) * | 2018-05-07 | 2018-11-09 | 昆明理工大学 | A kind of method of anode material for lithium-ion batteries coating modification |
| CN109768264A (en) * | 2019-03-06 | 2019-05-17 | 浙江工业大学 | A kind of preparation method of lithium titanate composite anode material |
| CN109880114A (en) * | 2019-03-12 | 2019-06-14 | 北京科技大学 | A kind of Ti-MOFs material and preparation method thereof using solvent structure |
| CN110165196A (en) * | 2019-06-13 | 2019-08-23 | 吉林大学 | A kind of NCM333With ZIF-8 composite positive pole and preparation method |
| CN110982083A (en) * | 2019-12-05 | 2020-04-10 | 浙江华恒复合材料有限公司 | Microporous metal organic framework material used as getter of vacuum insulation board and synthetic method thereof |
| CN110982083B (en) * | 2019-12-05 | 2022-02-11 | 浙江华恒复合材料有限公司 | Microporous metal organic framework material used as getter of vacuum insulation board and synthetic method thereof |
| CN112968211A (en) * | 2021-02-05 | 2021-06-15 | 佛山仙湖实验室 | Sodium ion solid electrolyte and preparation method and application thereof |
| CN114784261A (en) * | 2022-06-21 | 2022-07-22 | 宜宾锂宝新材料有限公司 | Lithium battery positive electrode material and preparation method thereof |
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