CN106992289A - Synthesis method of lithium magnesium titanate chromate and application of lithium magnesium titanate chromate as negative electrode material of lithium ion battery - Google Patents
Synthesis method of lithium magnesium titanate chromate and application of lithium magnesium titanate chromate as negative electrode material of lithium ion battery Download PDFInfo
- Publication number
- CN106992289A CN106992289A CN201710247539.0A CN201710247539A CN106992289A CN 106992289 A CN106992289 A CN 106992289A CN 201710247539 A CN201710247539 A CN 201710247539A CN 106992289 A CN106992289 A CN 106992289A
- Authority
- CN
- China
- Prior art keywords
- lithium
- titanium
- magnesium
- solution
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 30
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 title abstract 3
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 title abstract 3
- 239000007773 negative electrode material Substances 0.000 title abstract 2
- 238000001308 synthesis method Methods 0.000 title 1
- 239000010936 titanium Substances 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 41
- 239000011777 magnesium Substances 0.000 claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- -1 lithium titanium magnesium chromate Chemical compound 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 239000011651 chromium Substances 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 57
- 238000010189 synthetic method Methods 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 238000000034 method Methods 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 229910009866 Ti5O12 Inorganic materials 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 206010016766 flatulence Diseases 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
-
- 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
- H01M4/626—Metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for synthesizing lithium magnesium titanate chromate and application thereof as a lithium ion battery cathode material, firstly dissolving a titanium source in an alcohol solution to form a titanium solution; adding a lithium source, a magnesium source and a chromium source into deionized water to prepare a mixed solution; adding the mixed solution into the titanium solution under the stirring state, and fully and uniformly mixing to obtain a composite solution; transferring the composite solution into a reaction kettle, heating for at least 24h at the temperature of 170-190 ℃, and performing suction filtration and drying to obtain a precursor; calcining the precursor for at least 12h under the conditions of air atmosphere and temperature of 500-700 ℃ to obtain the lithium titanium magnesium chromate. The lithium battery prepared by using the lithium titanium magnesium chromate prepared by the invention as the negative electrode material of the lithium battery has good rate capability and cycling stability.
Description
Technical field
The invention belongs to synthetic method and its conduct of technical field of lithium ion, more particularly to a kind of titanium magnesium lithium chromate
The application of lithium ion battery negative material.
Background technology
With expanding economy, people increasingly increase the demand of energy.For a long time, the fossil fuel such as coal, oil
It is the main source that the mankind obtain energy, but these energy can discharge substantial amounts of pernicious gas while obtaining, to environment
Bring great harm.In order to solve the challenge that lack of energy and environmental pollution are brought to the mankind, the mankind must Speeding up development
With the paces using environmental protection and reproducible new energy.In numerous battery products, lithium ion battery is due to energy
Metric density is high, have extended cycle life, stable operating voltage, memory-less effect, can fast charging and discharging and it is pollution-free the advantages of and by
The favor of people.
In the early 1990s, Sony corporation of Japan take the lead in developing negative material using stone tar as lithium battery,
LiCoO2It is used as the lithium ion battery of anode material of lithium battery.This mode not only increases the security of lithium ion battery and filled
The discharge cycles life-span, and open the market of lithium ion battery.
It is well known that the quality of battery material performance determines the overall performance of lithium ion battery.Therefore development of new is high
The lithium battery material of specific energy is always the study hotspot of lithium ion battery.The negative material of lithium ion battery is in charge and discharge process
The middle carrier as lithium ion, it appears particularly important.From the development of lithium ion battery, the progress of negative material is to lithium
The development of ion battery plays conclusive effect.
1996, Canadian scholar K.Zaghib was proposed from lithium titanate as negative material and high-voltage anode first
Material constitutes lithium-ions battery (K.Zaghib, Solid state lithium ion batteries using carbon
or an oxide as negative electrode,Proceedings of Lithium Polymer Batteries
(ISBN 1 56,677 167 6)), or constitute electrochemical mixed capacitor with carbon electrode.Wherein, the lithium titanate of spinel-type
(Li4Ti5O12) there is higher workbench (1.55V vs.Li+/ Li), Li dendrite will not be produced in charge and discharge process, and
With good security performance；And generation passivating film is needed unlike carbon material in charging process, this is conducive to electrolysis
Matter is fully contacted with active material.Li4Ti5O12Material is during lithium ion is deviate from and be embedded, the change of lattice constant
Only 0.001, therefore Li4Ti5O12It is a kind of " zero strain " material.The plurality of advantages of lithium titanate makes it dynamic in electric automobile, mixing
The field such as power automobile and energy-storage battery is with a wide range of applications.But, Li4Ti5O12The electronic conductivity of material is low to be caused
Its chemical property under high magnification is poor, and can produce flatulence problem in battery charge and discharge process, and these are all seriously
The cycle life of battery is have impact on, and limits the practical application of lithium titanate.
In order to adapt to the growth requirement of battery, it is necessary to develop the negative material of new metatitanic acid salt system.New negative pole material
Material is capable of the electronic conductivity of high degree raising lithium titanate material, improves its high rate performance, while improving to a certain extent
Its flatulence problem.This high conductivity, the titanate material of low flatulence are in lithium ion battery energy storage field and start and stop field of power supplies
With very big application prospect.
The content of the invention：
It is it is an object of the invention to provide a kind of synthetic method of new titanium magnesium lithium chromate and its negative as lithium ion battery
The application of pole material.
A kind of synthetic method of titanium magnesium lithium chromate, its step is as follows：
(1) titanium source is dissolved in alcoholic solution and forms titanium solution；
(2) lithium source, magnesium source, chromium source are added in deionized water, is configured to mixed solution；
(3) under stirring, mixed solution is added in titanium solution, uniform composite solution is sufficiently mixed；
(4) composite solution is transferred in reactor, at least 24h is heated under the conditions of 170-190 DEG C, is dried by suction filtration
After obtain presoma；
(5) by presoma in air atmosphere, temperature be 500-700 DEG C under conditions of calcine at least 12h, obtain negative pole material
Expect titanium salt.
Further scheme, the molecular formula of the negative material titanium salt is Li4-xTi4MgxCrO12, wherein 0.9≤x≤1.1.
Further scheme, the titanium, lithium, magnesium, the element molal weight ratio of chromium are 4：(3-3.15)：(0.95-1.05)：1.
Further scheme, the titanium source is the one or more in butyl titanate, titanium sulfate, titanium tetrachloride.
Further scheme, the lithium source is one kind or many in lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium oxalate
Kind.
Further scheme, the magnesium source is the one or more in magnesium acetate, magnesium chloride, magnesium nitrate, magnesium sulfate.
Further scheme, the chromium source is one or both of chromic nitrate, chromium acetate.
Further scheme, the alcoholic solution is the one or more in ethanol, methanol, isopropanol.
Another goal of the invention of the present invention is to provide the application of titanium magnesium lithium chromate prepared by above-mentioned synthetic method, the titanium
Magnesium lithium chromate is used as lithium ion battery negative material.
The present invention synthesizes Li by hydro-thermal method4Ti5O12While material, by Mg2+And Cr3+Titanium is mixed according to certain ratio
In the lattice structure of sour lithium, the novel anode material synthesized with such a method is still spinel structure.Ionic radius is larger
Metal cation is introduced into lattice structure, has on the one hand widened the diffusion admittance of lithium ion, reduces the diffusional resistance of lithium ion
So as to improve the ionic conductivity of material；On the other hand, the Li of+1 valency+The Mg of quilt+divalent2+Substitution, so that the lattice knot of material
Structure produces defect, and this is conducive to the electronic conductivity for improving material.Therefore, the new titanate negative material that the present invention is synthesized
Li4-xTi4MgxCrO12(0.9≤x≤1.1) can improve the electronic conductivity of material to a certain extent.
Titanate negative material Li prepared by the present invention4-xTi4MgxCrO12(0.9≤x≤1.1) are assembled into button-shaped electricity
Pond, is tested the charge-discharge performance of the battery, test result shows under 0.2C, 0.5C, 1C, 3C multiplying power：0.2C's
Specific discharge capacity is 162.9-164.7mAh/g, and 0.5C specific discharge capacity is 155.8-157.8mAh/g, 1C electric discharge specific volume
Measure as 147.0-148.5mAh/g, 3C specific discharge capacity is 126.7-128.3mAh/g；Under 1C multiplying powers, after 20 circulations, hold
Amount conservation rate reaches 97.3-98.2%.Test result is above the lithium titanate material synthesized under the same terms, is indicated above the lithium
Ion battery cathode material Li4-xTi4MgxCrO12(x=1) there is good chemical property.
So, beneficial effects of the present invention
Titanium magnesium lithium chromate Li prepared by the present invention4-xTi4MgxCrO12(0.9≤x≤1.1) can be used as lithium ion battery anode material
Material, and still keep the spinel structure of lithium titanate；The primary particle size of material is carried in nanoscale, the nanoparticle size of material
The high contact area of electrolyte and active material, shortens Li+Diffusion path.
In addition ,+divalent Mg2+It instead of the Li of+1 valency+, be conducive to introducing Lacking oxygen in material internal, so as to add material
Electron transfer path, improve material electronic conductivity.
Brief description of the drawings
Fig. 1 is lithium ion battery negative material Li prepared by embodiment 14-xTi4MgxCrO12(x=1) XRD spectrum；
Fig. 2 is lithium ion battery negative material Li prepared by embodiment 14-xTi4MgxCrO12And comparative example 1 is made (x=1)
Standby Li4Ti5O12High rate performance collection of illustrative plates；
Fig. 3 is the gained lithium ion battery negative material Li of embodiment 14-xTi4MgxCrO12(x=1) and prepared by comparative example 1
Li4Ti5O12Cycle performance collection of illustrative plates.
Embodiment
Below by specific embodiment and the present invention is described in detail with reference to accompanying drawing, but it is not intended to limit the present invention.
The preparation of battery and the method for testing of chemical property
(1) preparation of battery cathode sheet
By the lithium ion battery negative material Li of acquisition4-xTi4MgxCrO12It is (0.9≤x≤1.1), conductive carbon powder, organic viscous
Knot agent gathers inclined tetrafluoroethene (PVDF) according to mass ratio 80：10：10 ratio is mixed, and slurry is formed after being sufficiently stirred for, and is applied
Aluminium foil surface is overlying on, after drying, battery cathode sheet is obtained through roll-in cut-parts；
(2) battery assembling and performance test, are assessed using 2016 type half-cells and obtain lithium ion battery negative material Li4- xTi4MgxCrO12The chemical property of (0.9≤x≤1.1).
The battery cathode sheet rolled is stamped into after the disk of 12 millimeters of diameter, its quality of precise, according to
Fang Zucheng calculates the quality of the active material in negative plate, using 18 millimeters of PE barrier films of diameter, uses 16 millimeters of diameter
Metal lithium sheet is as positive pole, and battery can be tested by being assembled into meter Kai Luo that glove box；The specific capacity test of battery uses Shenzhen
Xin Wei companies cell tester (new prestige BTS7.5.6) is carried out, and multiple loop test is carried out under the conditions of 0.2C, 0.5C, 1C, 3C.
Embodiment 1
A kind of titanium magnesium lithium chromate Li4-xTi4MgxCrO12The synthetic method of (0.9≤x≤1.1), it includes as follows：
(1) by 0.04mol butyl titanate and 17ml ethanol, it is configured to solution A；
(2) by 0.0313mol lithium hydroxide, 0.01mol magnesium acetate, 0.01mol chromic nitrates and 22ml deionization
Water, is configured to solution B；
(3) under stirring, solution B is added in solution A, solution C is obtained after being sufficiently mixed uniformly；
(4) solution C is transferred in the reactor of polytetrafluoroethylene (PTFE), heats 24h under the conditions of 180 DEG C, dried by suction filtration
After obtain presoma；
(5) by presoma powder in air atmosphere, temperature obtains Li to calcine 12h under conditions of 600 DEG C4- xTi4MgxCrO12(x=1) negative material.
The lithium ion battery negative material Li of above-mentioned gained4-xTi4MgxCrO12(x=1), using X-ray diffractometer (XRD,
Rigaku Rigaku) detected, its XRD as shown in figure 1, through comparison XRD standard databases, do not inquire on
Li4-xTi4MgxCrO12(x=1) thing phase information, shows the Li obtained in the present invention4-xTi4MgxCrO12(x=1) it is a kind of new
Section bar material, does not there is literature research report before this.By the spectral line in Fig. 1 compared with the spectral line of other materials, find the spectrogram with
Li4Ti5O12Structure coincide, illustrate Li4-xTi4MgxCrO12And Li (x=1)4Ti5O12With similar crystal structure, show institute
The lithium ion battery negative material Li obtained4-xTi4MgxCrO12(x=1) spinel structure is belonged to.It is good that this structure has material
Cyclical stability.
By the lithium ion battery negative material Li of above-mentioned gained4-xTi4MgxCrO12(x=1), assembled using half-cell method
Into button-shaped 2016 battery, tested respectively under 0.2C, 0.5C, 1C and 3C multiplying power, chemical property collection of illustrative plates such as Fig. 2 institutes of gained
Show, from figure 2 it can be seen that 0.2C specific discharge capacity is 164.7mAh/g, 0.5C specific discharge capacity is 157.8mAh/g,
1C specific discharge capacity is 148.5mAh/g, and 3C specific discharge capacity is 128.3mAh/g.Under 1C multiplying powers, after 20 circulations, hold
Amount conservation rate reaches 98.2%, and test result is above the lithium titanate material synthesized under the same terms.
Above-mentioned test result shows, the lithium ion battery negative material Li obtained by the present invention4-xTi4MgxCrO12(x=1) have
There is good high rate performance and cyclical stability, can be in energy-storage battery and 48V start and stop field of power supplies applications.
Comparative example 1
A kind of titanium magnesium lithium chromate Li4-xTi4MgxCrO12The synthetic method of (0.9≤x≤1.1), it includes as follows：
(1) 0.04mol butyl titanate and 17ml ethanol are weighed, solution A is configured to；
(2) 0.0313mol lithium hydroxide and 22ml deionized water are weighed, solution B is configured to；
(3) under stirring, solution B is added in solution A, solution C is obtained after being sufficiently mixed uniformly；
(4) solution C is transferred in the reactor of polytetrafluoroethylene (PTFE), heats 24h under the conditions of 180 DEG C, dried by suction filtration
After obtain presoma；
(5) by presoma powder in air atmosphere, temperature obtains Li to calcine 12h under conditions of 600 DEG C4Ti5O12It is negative
Pole material.
By the lithium ion battery negative material Li prepared by embodiment 14-xTi4MgxCrO12And comparative example 1 is made (x=1)
Standby Li4Ti5O12, button-shaped 2016 battery is assembled into using half-cell method respectively, respectively in 0.2C, 0.5C, 1C and 3C times
Tested under rate, its chemical property collection of illustrative plates is as shown in Fig. 2 from figure 2 it can be seen that Li prepared by the embodiment of the present invention 14- xTi4MgxCrO12(x=1) it is 164.7mAh/g in 0.2C specific discharge capacity, 0.5C specific discharge capacity is 157.8mAh/g,
1C specific discharge capacity is 148.5mAh/g, and 3C specific discharge capacity is 128.3mAh/g.And prepared by comparative example 1
Li4Ti5O12, it is 158.2mAh/g in 0.2C specific discharge capacity, 0.5C specific discharge capacity is 146.5mAh/g, 1C electric discharge
Specific capacity is 139.1mAh/g, and 3C specific discharge capacity is 116.0mAh/g.
Cycle performance collection of illustrative plates is as shown in figure 3, the Li that wherein prepared by the embodiment of the present invention 14-xTi4MgxCrO12(x=1) in 1C
Under multiplying power, after 20 circulations, capability retention reaches 98.2%；And Li prepared by comparative example 14Ti5O12, under 1C multiplying powers, 20
After secondary circulation, capability retention reaches 95.3%.
So Li prepared by the present invention4-xTi4MgxCrO12The chemical property and cycle performance of (0.9≤x≤1.1) are high
In the lithium titanate material synthesized under the same terms.
Embodiment 2
A kind of titanium magnesium lithium chromate Li4-xTi4MgxCrO12The synthetic method of (0.9≤x≤1.1), it includes as follows：
(1) 0.04mol titanium sulfate and 15ml methanol are weighed, certain density solution A is configured to.
(2) 0.03mol lithium carbonate is weighed, the deionization of 0.0105mol magnesium chloride, 0.01mol chromic nitrates and 25ml
Water, is configured to certain density solution B.
(3) under stirring, solution B is added in solution A, solution C is obtained after being sufficiently mixed uniformly.
(4) solution C is transferred in the reactor of polytetrafluoroethylene (PTFE), heats 24h under the conditions of 170 DEG C, dried by suction filtration
After obtain presoma.
(5) by presoma powder in air atmosphere, temperature obtains Li to calcine 12h under conditions of 500 DEG C4- xTi4MgxCrO12(x=1.1) negative material.
Lithium ion battery negative material Li obtained by the present invention4-xTi4MgxCrO12(x=1.1) there is well forthright again
Energy and cyclical stability, can be in energy-storage battery and 48V start and stop field of power supplies applications.
Embodiment 3
A kind of titanium magnesium lithium chromate Li4-xTi4MgxCrO12The synthetic method of (0.9≤x≤1.1), it includes as follows：
(1) 0.04mol titanium tetrachloride and 20ml isopropanol are first weighed, certain density solution A is configured to.
(2) and then 0.0315mol lithium nitrate is weighed, 0.0095mol magnesium nitrate, 0.01mol chromium acetates and 20ml
Deionized water, is configured to certain density solution B.
(3) under stirring, solution B is added in solution A, solution C is obtained after being sufficiently mixed uniformly.
(4) secondly solution C is transferred in the reactor of polytetrafluoroethylene (PTFE), 24h is heated under the conditions of 190 DEG C, by suction filtration
Presoma is obtained after drying.
(5) finally by presoma powder in air atmosphere, temperature be 700 DEG C under conditions of calcine 12h, obtain Li4- xTi4MgxCrO12(x=0.9) negative material.
Lithium ion battery negative material Li obtained by the present invention4-xTi4MgxCrO12(x=0.9) there is well forthright again
Energy and cyclical stability, can be in energy-storage battery and 48V start and stop field of power supplies applications.
Described above is only the citing of embodiments of the present invention, it is noted that for the ordinary skill of the art
For personnel, without departing from the technical principles of the invention, some improvement can also be made, these improvement also should be regarded as this
The protection domain of invention.
Claims (9)
1. a kind of synthetic method of titanium magnesium lithium chromate, it is characterised in that：Step is as follows：
（1）Titanium source is dissolved in alcoholic solution and forms titanium solution；
（2）Lithium source, magnesium source, chromium source are added in deionized water, mixed solution is configured to；
（3）Under stirring, mixed solution is added in titanium solution, uniform composite solution is sufficiently mixed；
（4）Composite solution is transferred in reactor, at least 24h is heated under the conditions of 170-190 DEG C, after suction filtration is dried
To presoma；
（5）By presoma in air atmosphere, temperature be 500-700 DEG C under conditions of calcine at least 12h, obtain titanium magnesium chromic acid
Lithium.
2. synthetic method according to claim 1, it is characterised in that：The molecular formula of the titanium magnesium lithium chromate is Li4- xTi4MgxCrO12, wherein 0.9≤x≤1.1.
3. synthetic method according to claim 1, it is characterised in that：The titanium, lithium, magnesium, the element molal weight ratio of chromium
For 4：（3-3.15）：（0.95-1.05）：1.
4. synthetic method according to claim 1, it is characterised in that：The titanium source is butyl titanate, titanium sulfate, tetrachloro
Change the one or more in titanium.
5. synthetic method according to claim 1, it is characterised in that：The lithium source is lithium hydroxide, lithium carbonate, acetic acid
One or more in lithium, lithium nitrate, lithium oxalate.
6. synthetic method according to claim 1, it is characterised in that：The magnesium source be magnesium acetate, magnesium chloride, magnesium nitrate,
One or more in magnesium sulfate.
7. synthetic method according to claim 1, it is characterised in that：The chromium source is one kind in chromic nitrate, chromium acetate
Or two kinds.
8. synthetic method according to claim 1, it is characterised in that：The alcoholic solution is in ethanol, methanol, isopropanol
It is one or more kinds of.
9. a kind of application of titanium magnesium lithium chromate prepared by synthetic method as claimed in claim 1, it is characterised in that：The titanium magnesium
Lithium chromate is used as lithium ion battery negative material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710247539.0A CN106992289A (en) | 2017-04-16 | 2017-04-16 | Synthesis method of lithium magnesium titanate chromate and application of lithium magnesium titanate chromate as negative electrode material of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710247539.0A CN106992289A (en) | 2017-04-16 | 2017-04-16 | Synthesis method of lithium magnesium titanate chromate and application of lithium magnesium titanate chromate as negative electrode material of lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106992289A true CN106992289A (en) | 2017-07-28 |
Family
ID=59416217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710247539.0A Pending CN106992289A (en) | 2017-04-16 | 2017-04-16 | Synthesis method of lithium magnesium titanate chromate and application of lithium magnesium titanate chromate as negative electrode material of lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106992289A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107742700A (en) * | 2017-09-15 | 2018-02-27 | 苏州思创源博电子科技有限公司 | A kind of preparation method of carbon coating titanium lithium composite negative pole material |
| CN107799734A (en) * | 2017-09-12 | 2018-03-13 | 苏州思创源博电子科技有限公司 | A kind of preparation method of ferro-aluminum doped titanic acid lithium titanate cathode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022461A (en) * | 2012-12-13 | 2013-04-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Rare-earth metal doped micro-nanometer lithium titanate cathode material and preparation method thereof |
| CN103151506A (en) * | 2013-03-12 | 2013-06-12 | 上海大学 | Preparation method of nanoscale zirconium-doped lithium titanate material |
| CN104201344A (en) * | 2014-09-05 | 2014-12-10 | 南开大学 | Preparation method of copper-doped Li4Ti5O12-TiO2 regulation and control composite material |
| CN104282886A (en) * | 2014-10-14 | 2015-01-14 | 江苏华东锂电技术研究院有限公司 | Carbon coating method for electrode active material of lithium ion battery |
-
2017
- 2017-04-16 CN CN201710247539.0A patent/CN106992289A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103022461A (en) * | 2012-12-13 | 2013-04-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Rare-earth metal doped micro-nanometer lithium titanate cathode material and preparation method thereof |
| CN103151506A (en) * | 2013-03-12 | 2013-06-12 | 上海大学 | Preparation method of nanoscale zirconium-doped lithium titanate material |
| CN104201344A (en) * | 2014-09-05 | 2014-12-10 | 南开大学 | Preparation method of copper-doped Li4Ti5O12-TiO2 regulation and control composite material |
| CN104282886A (en) * | 2014-10-14 | 2015-01-14 | 江苏华东锂电技术研究院有限公司 | Carbon coating method for electrode active material of lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| ZHENWEI ZHANG，ET AL.: "Hydrothermal synthesis of Zn-doped Li4Ti5O12 with improved high rate properties for lithium ion batteries", 《CERAMICS INTERNATIONAL》 * |
| 李南，等: "Li3Ti4CrMO12负极材料制备及其电化学性能", 《上海应用技术学院学报（自然科学版）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107799734A (en) * | 2017-09-12 | 2018-03-13 | 苏州思创源博电子科技有限公司 | A kind of preparation method of ferro-aluminum doped titanic acid lithium titanate cathode material |
| CN107742700A (en) * | 2017-09-15 | 2018-02-27 | 苏州思创源博电子科技有限公司 | A kind of preparation method of carbon coating titanium lithium composite negative pole material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106229498B (en) | Cathode material suitable for water-based metal ion battery and preparation method thereof | |
| CN106058222B (en) | Polymer carbonization in-situ coated ferric trifluoride composite cathode material and preparation method thereof | |
| CN108539190A (en) | The molybdenum trioxide of a kind of oxygen-containing vacancy and using it as the water system aluminium ion battery of negative electrode active material and their preparation method | |
| CN103427077B (en) | Ultrathin V2O5 nanosheet, and preparation method and application thereof | |
| CN107069079A (en) | A kind of solid state electrolyte and its preparation and application | |
| CN105845924B (en) | The preparation method of the lithium titanate nanometer sheet of Fluorin doped | |
| CN103700842B (en) | A kind of NiFe 2o 4/ C lithium ion battery cathode material and its preparation method | |
| CN107601579B (en) | The preparation method and its resulting materials of a kind of high-performance porous C o-Mn-O nanometer sheet material and application | |
| CN108598394A (en) | Carbon coating titanium phosphate manganese sodium micron ball and its preparation method and application | |
| CN107742712B (en) | A kind of conducting polymer coating-doping type anode material for lithium-ion batteries and its synthetic method | |
| CN106992295B (en) | A kind of preparation method of monodisperse alpha-ferric oxide nanometer sheet | |
| CN106340400B (en) | A kind of carbon coating rhombic system nano bar-shape Nb2O5Material and preparation method thereof | |
| CN109494357B (en) | Preparation and application of ferric fluoride doped nano titanium dioxide | |
| CN107293747A (en) | A kind of anode of magnesium ion battery material of magnesium position doping and preparation method thereof | |
| CN108281620B (en) | Preparation method of negative electrode material titanium dioxide of sodium-ion battery | |
| CN106992289A (en) | Synthesis method of lithium magnesium titanate chromate and application of lithium magnesium titanate chromate as negative electrode material of lithium ion battery | |
| CN107720822B (en) | A kind of preparation method of sea urchin shape anode material for lithium-ion batteries | |
| CN111628174B (en) | Synthesis method and application of titanium dioxide with halogen ions doped with titanium vacancies | |
| CN106099074A (en) | A kind of modified fluorinated ferrum nano composite anode material and its preparation method and application | |
| Li et al. | The research and synthesis of the cubic 2MnCO3@ ZnO applied as cathode material for zinc ion battery | |
| CN113628890B (en) | Bimetallic selenide composite Ti 3 C 2 Preparation method of material, product thereof and super capacitor | |
| CN109390569A (en) | A kind of sheet polypyrrole/redox graphene compound and preparation method thereof and the application as anode material for lithium-ion batteries | |
| CN113036230B (en) | Preparation method and application of lithium cobaltate soft package battery | |
| CN112259786B (en) | LiBH4-LiI-P2S5Ternary composite solid electrolyte and preparation method thereof | |
| CN106711438A (en) | Method for measuring and improving lithium ion battery performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170728 |
|
| RJ01 | Rejection of invention patent application after publication |