CN105280895A - Lithium ion battery cathode composite material and preparation method thereof - Google Patents
Lithium ion battery cathode composite material and preparation method thereof Download PDFInfo
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- CN105280895A CN105280895A CN201510578783.6A CN201510578783A CN105280895A CN 105280895 A CN105280895 A CN 105280895A CN 201510578783 A CN201510578783 A CN 201510578783A CN 105280895 A CN105280895 A CN 105280895A
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- lithium
- ion battery
- lithium ion
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000010406 cathode material Substances 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000012071 phase Substances 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 78
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 19
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 10
- 239000011240 wet gel Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-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
- 150000007524 organic acids Chemical class 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 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 compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 abstract 2
- 238000005303 weighing Methods 0.000 abstract 2
- 229910011312 Li3VO4 Inorganic materials 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000009831 deintercalation Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 32
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000536 complexating effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- -1 lithium titanate compound Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a lithium ion battery cathode composite material and a preparation method thereof, wherein the lithium ion cathode composite material is prepared according to a chemical formula xLi3VO4·(1-x)Li4Ti5O12(wherein x is more than or equal to 0.5 and less than or equal to 1) compounding according to the stoichiometric ratio; the preparation method comprises the following steps: weighing a lithium source and a vanadium source, and adding an additive and a solvent or a complexing agent and a solvent to form a solution or slurry A; weighing a lithium source and a titanium source, and adding an additive and a solvent or a complexing agent and a solvent to form a solution or slurry B; uniformly mixing A and B by a liquid phase or solid phase method, drying and sintering to obtain Li3VO4And Li4Ti5O12A two-phase composite. The composite material obtained by the invention is used as the lithium ion battery cathode material, and fully utilizes the characteristics that lithium vanadate has proper intercalation and deintercalation potential and considerable capacity, so that the composite material has higher coulombic efficiency, higher specific capacity and good rate capability.
Description
Technical field
The invention belongs to lithium battery material field, be specifically related to a kind of Li
3vO
4and Li
4ti
5o
12the lithium ion battery cathode material and its preparation method of two-phase compound.
Background technology
At present, graphite has higher stability because of it and cost performance is widely used in lithium ion battery cathode material, and its theoretical capacity is 372mAh/g, belongs to embedding and deviate from type ion cathode material lithium.But in charge and discharge process, the intercalation potential of graphite is lower than 0.1V (vsLi/Li
+), cause occurring that in cyclic process Li dendrite pierces through barrier film and causes battery short circuit, thus cause the potential safety hazard of power vehicle.In order to eliminate the appearance of this kind of phenomenon, the negative material that by effort for many years, researchers find that a kind of discharge platform is suitable for, capacity and graphite-phase are worked as.Within 2013, Japanese Scientists finds lithium vanadate (Li
3vO
4) negative material, its discharge potential is 0.5 ~ 1V (vsLi/Li
+), compared to graphite, there is higher discharge potential thus improve the security performance of battery, and relative to lithium titanate anode material, there is higher capacity, when matching with other positive electrodes, battery has wider discharge voltage, thus makes battery have higher capacity.
Research finds, lithium vanadate (Li
3vO
4) belong to ion conductor, there is very high ionic conductivity, but the very poor intimate insulator of its electron conduction, its chemical property is had a strong impact on, especially its cycle performance.In order to improve its conductivity, researchers start to carry out particle nanometer and surface modification treatment to lithium vanadate, the most conventional method introduces material with carbon element exactly to improve its conductivity, (the J.PowerSources2014 such as Liang, 252:244-247) carbon carries out to lithium vanadate coated, and (the NanoLett. such as Shi, 2013,13 (10): 4715 – 4720) adopt lithium vanadate and graphene film compound, lithium vanadate cycle performance is improved and all obtains good result.But can be formed on electrode with electrolyte face after being through material with carbon element process and form the same solid electrolyte interface film (SEI) with conventional carbon material, still can cause bad impact to the security performance of battery.
Summary of the invention
One of the object of the invention improves cycle performance and the security performance of material, carrys out satisfied following electric automobile industry to the requirement of electrokinetic cell long-life high safety performance; Two of the object of the invention is that the ratio by changing lithium vanadate and lithium titanate improves the capacity of negative material when other positive electrodes mate while improving circulating effect as far as possible, thus improves battery durable ability.
In order to arrive above object, the present invention intends being achieved by the following technical solutions.
A kind of composite cathode material of lithium ion battery, by Li
3vO
4and Li
4ti
5o
12two-phase is according to chemical formula xLi
3vO
4(1-x) Li
4ti
5o
12carry out compound, wherein 0.5≤x≤1.
Preferably, the preparation method of described composite cathode material of lithium ion battery, comprises the following steps:
(1) take lithium source and vanadium source according to mol ratio Li:V=3.0 ~ 3.2:1, add " additive and solvent " or " complexing agent and solvent " and form solution or slurry A afterwards;
(2) take lithium source and titanium source according to mol ratio Li:Ti=4.0 ~ 4.1:5, add " additive and solvent " or " complexing agent and solvent " and form solution or slurry B afterwards;
(3), after A and B being mixed by the method for liquid phase or solid phase, be warmed up to after 70-90 DEG C of evaporating solvent forms wet gel and transfer to air dry oven dry 12 ~ 48h under 80-120 DEG C of condition, obtain Li
3vO
4and Li
4ti
5o
12presoma;
(4) (3) are prepared presoma in Muffle furnace after 400-500 DEG C of pre-burning 3-5h with stove Temperature fall, take out sample through grinding after in 600 ~ 900 DEG C, sintering 6 ~ 12h obtain Li
3vO
4and Li
4ti
5o
12the lithium ion battery negative material of two-phase compound.
Preferably, described lithium source is one or both in lithium nitrate, lithium acetate, lithium hydroxide, lithium carbonate; Vanadium source is the one in ammonium metavanadate or vanadic oxide; Titanium source is one or both in butyl titanate, tetraethyl titanate, tetraisopropyl titanate, titanium dioxide, titanium tetrachloride.
Preferably, adopt the method for solid phase to mix in described step (3), additive during synthetic composite material is grinding aid; Described grinding aid is one or both in polymerized polyalcohol, polyalcohol amine, triethanolamine, triisopropanolamine, ethylene glycol, diethylene glycol.
Preferably, adopt the method for liquid phase to mix in described step (3), the complexing agent of synthetic composite material is organic acid; Described organic acid is the one or more combination in citric acid, glycine, salicylic acid, oxalic acid, adipic acid, ethylenediamine tetra-acetic acid.
Preferably, described solvent be deionized water, ethanol, ethylene glycol, acetone one or both.
Preferably, described sintering atmosphere is air.
Beneficial effect of the present invention is:
(1) Li
3vO
4and Li
4ti
5o
12be all containing lithium titanate cathode material, both one-tenth phase temperature close, therefore can adopt identical temperature to heat-treat to obtain the perfect two-phase composite material of crystallization by adding lithium source after vanadium source and titanium source are mixed;
(2) lithium vanadate obtained by the present invention and the composite material of lithium titanate have higher coulombic efficiency, higher specific capacity and good high rate performance as lithium ion battery negative material, take full advantage of lithium vanadate and there is the characteristic that current potential and considerable volume are deviate from suitable embedding, be expected to obtain extensive promotion and application in electrokinetic cell industry.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 synthesizes xLi
3vO
4(1-x) Li
4ti
5o
12the XRD collection of illustrative plates of composite material;
Fig. 2 is that embodiment 1 synthesizes xLi
3vO
4(1-x) Li
4ti
5o
12the SEM collection of illustrative plates of composite material;
Fig. 3 is that embodiment 1 synthesizes xLi
3vO
4(1-x) Li
4ti
5o
12the charging and discharging curve figure of composite material;
Fig. 4 is that embodiment 1 synthesizes xLi
3vO
4(1-x) Li
4ti
5o
12the cyclic curve figure of composite material.
Embodiment
In order to the present invention will be described in detail better, be below the method specific experiment process improving lithium vanadate lithium ion battery negative material cycle performance, embodiment adopts liquid phase method to be described, but the present invention is not limited to this.
Embodiment 1
(1) according to chemical formula xLi
3vO
4(1-x) Li
4ti
5o
12take citric acid 12.61g to be dissolved in 300mL deionized water to form water white citric acid solution as x=0.75, take 3.51g ammonium metavanadate according to mol ratio Li:V=3.0 ~ 3.2:1 slowly to join in citric acid solution and form claret clear solution, normal temperature lower magnetic force adds 9.365g Lithium acetate dihydrate as lithium source after stirring the abundant complexing of 1h, forms clear solution A after continuing to stir 0.5h;
(2) as x=0.75, taking 17.36g butyl titanate according to mol ratio Li:Ti=4.0 ~ 4.1:5 is dissolved in 100mL absolute ethyl alcohol, stir 2h under normal temperature and form uniform butyl titanate ethanolic solution, then taking 13.45g Lithium acetate dihydrate adds wherein, forms shallow yellow transparent solution B after continuing to stir 1h;
(3) after preparing solution A and B, solution A is added drop-wise in solution B with the speed of 20mL/min and is slowly hydrolyzed formation yellow-green soln, be warmed up to after 80 DEG C of evaporating solvents form wet gels and transfer to the dry 24h of 120 DEG C of air dry ovens, obtain 0.75Li
3vO
40.25Li
4ti
5o
12composite material precursor;
(4) (3) are prepared presoma in Muffle furnace with after 3 DEG C/min heating rate, 450 DEG C of pre-burning 4h with stove Temperature fall, take out sample through grinding after 800 DEG C sintering 10h obtain 0.75Li
3vO
40.25Li
4ti
5o
12composite cathode material of lithium ion battery.
Embodiment 2
(1) according to chemical formula xLi
3vO
4(1-x) Li
4ti
5o
12take citric acid 12.61g to be dissolved in 300mL deionized water to form water white citric acid solution as x=0.75, take 3.51g ammonium metavanadate according to mol ratio Li:V=3.0 ~ 3.2:1 slowly to join in citric acid solution and form claret clear solution, normal temperature lower magnetic force adds 9.365g Lithium acetate dihydrate as lithium source after stirring the abundant complexing of 1h, forms clear solution A after continuing to stir 0.5h;
(2) as x=0.75, taking 17.36g butyl titanate according to mol ratio Li:Ti=4.0 ~ 4.1:5 is dissolved in 100mL absolute ethyl alcohol, stir 2h under normal temperature and form uniform butyl titanate ethanolic solution, then taking 13.45g Lithium acetate dihydrate adds wherein, forms shallow yellow transparent solution B after continuing to stir 1h;
(3) after preparing solution A and B, solution A is added drop-wise in solution B with the speed of 20mL/min and is slowly hydrolyzed formation yellow-green soln, be warmed up to after 80 DEG C of evaporating solvents form wet gels and transfer to the dry 24h of 120 DEG C of air dry ovens, obtain 0.75Li
3vO
40.25Li
4ti
5o
12composite material precursor;
(4) (3) are prepared presoma in Muffle furnace with after 3 DEG C/min heating rate, 450 DEG C of pre-burning 4h with stove Temperature fall, take out sample through grinding after 700 DEG C sintering 10h obtain 0.75Li
3vO
40.25Li
4ti
5o
12composite cathode material of lithium ion battery.
Embodiment 3
(1) according to chemical formula xLi
3vO
4(1-x) Li
4ti
5o
12take citric acid 12.61g to be dissolved in 300mL deionized water to form water white citric acid solution as x=0.75, take 3.51g ammonium metavanadate according to mol ratio Li:V=3.0 ~ 3.2:1 slowly to join in citric acid solution and form claret clear solution, normal temperature lower magnetic force adds 9.365g Lithium acetate dihydrate as lithium source after stirring the abundant complexing of 1h, forms clear solution A after continuing to stir 0.5h;
(2) as x=0.75, taking 17.36g butyl titanate according to mol ratio Li:Ti=4.0 ~ 4.1:5 is dissolved in 100mL absolute ethyl alcohol, stir 2h under normal temperature and form uniform butyl titanate ethanolic solution, then taking 13.45g Lithium acetate dihydrate adds wherein, forms shallow yellow transparent solution B after continuing to stir 1h;
(3) after preparing solution A and B, solution A is added drop-wise in solution B with the speed of 20mL/min and is slowly hydrolyzed formation yellow-green soln, be warmed up to after 80 DEG C of evaporating solvents form wet gels and transfer to the dry 12h of 80 DEG C of air dry ovens, obtain 0.75Li
3vO
40.25Li
4ti
5o
12composite material precursor;
(4) (3) are prepared presoma in Muffle furnace with after 3 DEG C/min heating rate, 450 DEG C of pre-burning 4h with stove Temperature fall, take out sample through grinding after 900 DEG C sintering 10h obtain 0.75Li
3vO
40.25Li
4ti
5o
12composite cathode material of lithium ion battery.
Embodiment 4
(1) according to chemical formula xLi
3vO
4(1-x) Li
4ti
5o
12take citric acid 12.61g to be dissolved in 300mL deionized water to form water white citric acid solution as x=0.75, take 3.51g ammonium metavanadate according to mol ratio Li:V=3.0 ~ 3.2:1 slowly to join in citric acid solution and form claret clear solution, normal temperature lower magnetic force adds 9.365g Lithium acetate dihydrate as lithium source after stirring the abundant complexing of 1h, forms clear solution A after continuing to stir 0.5h;
(2) as x=0.75, taking 17.36g butyl titanate according to mol ratio Li:Ti=4.0 ~ 4.1:5 is dissolved in 100mL absolute ethyl alcohol, stir 2h under normal temperature and form uniform butyl titanate ethanolic solution, then taking 13.45g Lithium acetate dihydrate adds wherein, forms shallow yellow transparent solution B after continuing to stir 1h;
(3) after preparing solution A and B, solution A is added drop-wise in solution B with the speed of 20mL/min and is slowly hydrolyzed formation yellow-green soln, be warmed up to after 80 DEG C of evaporating solvents form wet gels and transfer to the dry 24h of 120 DEG C of air dry ovens, obtain 0.75Li
3vO
40.25Li
4ti
5o
12composite material precursor;
(4) (3) are prepared presoma in Muffle furnace with after 3 DEG C/min heating rate, 450 DEG C of pre-burning 4h with stove Temperature fall, take out sample through grinding after 800 DEG C sintering 8h obtain 0.75Li
3vO
40.25Li
4ti
5o
12composite cathode material of lithium ion battery.
Embodiment 5
(1) according to chemical formula xLi
3vO
4(1-x) Li
4ti
5o
12take citric acid 12.61g to be dissolved in 300mL deionized water to form water white citric acid solution as x=0.75, take 3.51g ammonium metavanadate according to mol ratio Li:V=3.0 ~ 3.2:1 slowly to join in citric acid solution and form claret clear solution, normal temperature lower magnetic force adds 9.365g Lithium acetate dihydrate as lithium source after stirring the abundant complexing of 1h, forms clear solution A after continuing to stir 0.5h;
(2) as x=0.75, taking 17.36g butyl titanate according to mol ratio Li:Ti=4.0 ~ 4.1:5 is dissolved in 100mL absolute ethyl alcohol, stir 2h under normal temperature and form uniform butyl titanate ethanolic solution, then taking 13.45g Lithium acetate dihydrate adds wherein, forms shallow yellow transparent solution B after continuing to stir 1h;
(3) after preparing solution A and B, solution A is added drop-wise in solution B with the speed of 20mL/min and is slowly hydrolyzed formation yellow-green soln, be warmed up to after 80 DEG C of evaporating solvents form wet gels and transfer to the dry 24h of 100 DEG C of air dry ovens, obtain 0.75Li
3vO
40.25Li
4ti
5o
12composite material precursor;
(4) (3) are prepared presoma in Muffle furnace with after 3 DEG C/min heating rate, 450 DEG C of pre-burning 4h with stove Temperature fall, take out sample through grinding after 700 DEG C sintering 12h obtain 0.75Li
3vO
40.25Li
4ti
5o
12composite cathode material of lithium ion battery.
Embodiment 6
(1) according to chemical formula xLi
3vO
4(1-x) Li
4ti
5o
12take citric acid 13.45g to be dissolved in 300mL deionized water to form water white citric acid solution as x=0.8, take 3.73g ammonium metavanadate according to mol ratio Li:V=3.0 ~ 3.2:1 slowly to join in citric acid solution and form claret clear solution, normal temperature lower magnetic force adds 9.99g Lithium acetate dihydrate as lithium source after stirring the abundant complexing of 1h, forms clear solution A after continuing to stir 0.5h;
(2) as x=0.8, taking 13.89g butyl titanate according to mol ratio Li:Ti=4.0 ~ 4.1:5 is dissolved in 100mL absolute ethyl alcohol, stir 2h under normal temperature and form uniform butyl titanate ethanolic solution, then taking 10.76g Lithium acetate dihydrate adds wherein, forms shallow yellow transparent solution B after continuing to stir 1h;
(3) after preparing solution A and B, solution A is added drop-wise in solution B with the speed of 20mL/min and is slowly hydrolyzed formation yellow-green soln, be warmed up to after 80 DEG C of evaporating solvents form wet gels and transfer to the dry 24h of 120 DEG C of air dry ovens, obtain 0.8Li
3vO
40.2Li
4ti
5o
12composite material precursor;
(4) (3) are prepared presoma in Muffle furnace with after 3 DEG C/min heating rate, 450 DEG C of pre-burning 4h with stove Temperature fall, take out sample through grinding after 800 DEG C sintering 10h obtain 0.8Li
3vO
40.2Li
4ti
5o
12composite cathode material of lithium ion battery.
Embodiment 7
(1) according to chemical formula xLi
3vO
4(1-x) Li
4ti
5o
12take citric acid 13.45g to be dissolved in 300mL deionized water to form water white citric acid solution as x=0.8, take 3.73g ammonium metavanadate according to mol ratio Li:V=3.0 ~ 3.2:1 slowly to join in citric acid solution and form claret clear solution, normal temperature lower magnetic force adds 9.99g Lithium acetate dihydrate as lithium source after stirring the abundant complexing of 1h, forms clear solution A after continuing to stir 0.5h;
(2) as x=0.8, taking 13.89g butyl titanate according to mol ratio Li:Ti=4.0 ~ 4.1:5 is dissolved in 100mL absolute ethyl alcohol, stir 2h under normal temperature and form uniform butyl titanate ethanolic solution, then taking 10.76g Lithium acetate dihydrate adds wherein, forms shallow yellow transparent solution B after continuing to stir 1h;
(3) after preparing solution A and B, solution A is added drop-wise in solution B with the speed of 20mL/min and is slowly hydrolyzed formation yellow-green soln, be warmed up to after 80 DEG C of evaporating solvents form wet gels and transfer to the dry 24h of 120 DEG C of air dry ovens, obtain 0.8Li
3vO
40.2Li
4ti
5o
12composite material precursor;
(4) (3) are prepared presoma in Muffle furnace with after 3 DEG C/min heating rate, 450 DEG C of pre-burning 4h with stove Temperature fall, take out sample through grinding after 700 DEG C sintering 12h obtain 0.8Li
3vO
40.2Li
4ti
5o
12composite cathode material of lithium ion battery.
Embodiment 8
(1) according to chemical formula xLi
3vO
4(1-x) Li
4ti
5o
12take citric acid 13.45g to be dissolved in 300mL deionized water to form water white citric acid solution as x=8, take 3.73g ammonium metavanadate according to mol ratio Li:V=3.0 ~ 3.2:1 slowly to join in citric acid solution and form claret clear solution, normal temperature lower magnetic force adds 9.99g Lithium acetate dihydrate as lithium source after stirring the abundant complexing of 1h, forms clear solution A after continuing to stir 0.5h;
(2) as x=8, taking 13.89g butyl titanate according to mol ratio Li:Ti=4.0 ~ 4.1:5 is dissolved in 100mL absolute ethyl alcohol, stir 2h under normal temperature and form uniform butyl titanate ethanolic solution, then taking 10.76g Lithium acetate dihydrate adds wherein, forms shallow yellow transparent solution B after continuing to stir 1h;
(3) after preparing solution A and B, solution A is added drop-wise in solution B with the speed of 20mL/min and is slowly hydrolyzed formation yellow-green soln, be warmed up to after 80 DEG C of evaporating solvents form wet gels and transfer to the dry 24h of 100 DEG C of air dry ovens, obtain 0.8Li
3vO
40.2Li
4ti
5o
12composite material precursor;
(4) will (3) prepare presoma in Muffle furnace with after 3 DEG C/min heating rate, 450 DEG C of pre-burning 4h with stove Temperature fall, take out sample through grinding after 900 DEG C sintering 8h obtain 0.8Li
3vO
40.2Li
4ti
5o
12composite cathode material of lithium ion battery.
By reference to the accompanying drawings, with embodiment 1,0.75Li prepared by the present invention is described
3vO
40.25Li
4ti
5o
12the thing of composite material characterizes and chemical property mutually:
Fig. 1 is 0.75Li prepared by embodiment 1
3vO
40.25Li
4ti
5o
12the XRD collection of illustrative plates of composite material, mainly comprises Li from analysis result composite material
3vO
4phase and Li
4ti
5o
12phase, both diffraction maximums are all comparatively strong, and the degree of crystallinity of illustrative material is higher.In addition, some TiO are had
2exist mutually, TiO in sintering process is described
2be not converted into Li completely
4ti
5o
12phase.
Fig. 2 is 0.75Li prepared by embodiment 1
3vO
40.25Li
4ti
5o
12the SEM collection of illustrative plates of composite material, is mainly ganoid spheric granules from analysis result composite material, and the domain size distribution of material is 200nm ~ 3 μm, without obvious duct between particle, piles up closely knit.
Fig. 3 is 0.75Li prepared by embodiment 1
3vO
40.25Li
4ti
5o
12the first charge-discharge curve chart of composite material, contrasted by compound anterioposterior curve, after lithium titanate compound, the charge and discharge platform change of curve obviously, the capacity of material plays higher, find that below 1.0V material discharging platform is mild simultaneously, the main capacity of material, at more than 0.1V, is conducive to the battery security improving material.
Fig. 4 is 0.75Li prepared by embodiment 1
3vO
40.25Li
4ti
5o
12the cyclic curve figure of composite material, by the contrast of compound anterioposterior curve, after lithium titanate compound, the cycle performance of material is significantly improved, and the capability retention through 150 recycled material also remains on more than 80%.
Claims (7)
1. a composite cathode material of lithium ion battery, is characterized in that: by Li
3vO
4and Li
4ti
5o
12two-phase is according to chemical formula xLi
3vO
4(1-x) Li
4ti
5o
12carry out compound, wherein 0.5≤x≤1.
2. a preparation method for composite cathode material of lithium ion battery, is characterized in that, comprises the following steps:
(1) take lithium source and vanadium source according to mol ratio Li:V=3.0 ~ 3.2:1, add " additive and solvent " or " complexing agent and solvent " and form solution or slurry A afterwards;
(2) take lithium source and titanium source according to mol ratio Li:Ti=4.0 ~ 4.1:5, add " additive and solvent " or " complexing agent and solvent " and form solution or slurry B afterwards;
(3), after A and B being mixed by the method for liquid phase or solid phase, be warmed up to after 70-90 DEG C of evaporating solvent forms wet gel and transfer to air dry oven dry 12 ~ 48h under 80-120 DEG C of condition, obtain Li
3vO
4and Li
4ti
5o
12presoma;
(4) (3) are prepared presoma in Muffle furnace after 400-500 DEG C of pre-burning 3-5h with stove Temperature fall, take out sample through grinding after in 600 ~ 900 DEG C, sintering 6 ~ 12h obtain Li
3vO
4and Li
4ti
5o
12the lithium ion battery negative material of two-phase compound.
3. the preparation method of composite cathode material of lithium ion battery according to claim 2, is characterized in that, described lithium source is one or both in lithium nitrate, lithium acetate, lithium hydroxide, lithium carbonate; Vanadium source is the one in ammonium metavanadate or vanadic oxide; Titanium source is one or both in butyl titanate, tetraethyl titanate, tetraisopropyl titanate, titanium dioxide, titanium tetrachloride.
4. the preparation method of composite cathode material of lithium ion battery according to claim 2, is characterized in that, adopt the method for solid phase to mix in described step (3), additive during synthetic composite material is grinding aid; Described grinding aid is one or both in polymerized polyalcohol, polyalcohol amine, triethanolamine, triisopropanolamine, ethylene glycol, diethylene glycol.
5. the preparation method of composite cathode material of lithium ion battery according to claim 2, is characterized in that, adopt the method for liquid phase to mix in described step (3), the complexing agent of synthetic composite material is organic acid; Described organic acid is the one or more combination in citric acid, glycine, salicylic acid, oxalic acid, adipic acid, ethylenediamine tetra-acetic acid.
6. the preparation method of composite cathode material of lithium ion battery according to claim 2, is characterized in that, described solvent be deionized water, ethanol, ethylene glycol, acetone one or both.
7. the preparation method of composite cathode material of lithium ion battery according to claim 2, is characterized in that, described sintering atmosphere is air.
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Cited By (4)
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| CN105720254A (en) * | 2016-03-02 | 2016-06-29 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon-coated lithium vanadate serving as negative electrode material of lithium ion battery |
| CN110323433A (en) * | 2019-07-10 | 2019-10-11 | 银隆新能源股份有限公司 | A kind of lithium titanate composite material and preparation method thereof, lithium ion battery and preparation method thereof |
| CN111033858A (en) * | 2017-08-30 | 2020-04-17 | 株式会社村田制作所 | Co-fired forming all-solid-state battery |
| CN111969189A (en) * | 2020-08-21 | 2020-11-20 | 贵州梅岭电源有限公司 | Lithium ion battery composite negative electrode material and preparation method thereof |
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| CN103794772A (en) * | 2012-10-30 | 2014-05-14 | 株式会社东芝 | Active material |
| CN104779364A (en) * | 2015-03-31 | 2015-07-15 | 中新能科技发展有限公司 | Anode of lithium ion battery, preparation method of anode and lithium ion battery |
| CN105810928A (en) * | 2014-12-30 | 2016-07-27 | 微宏动力系统（湖州）有限公司 | Biphase negative electrode material for lithium ion secondary battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103794772A (en) * | 2012-10-30 | 2014-05-14 | 株式会社东芝 | Active material |
| CN105810928A (en) * | 2014-12-30 | 2016-07-27 | 微宏动力系统（湖州）有限公司 | Biphase negative electrode material for lithium ion secondary battery and preparation method thereof |
| CN104779364A (en) * | 2015-03-31 | 2015-07-15 | 中新能科技发展有限公司 | Anode of lithium ion battery, preparation method of anode and lithium ion battery |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105720254A (en) * | 2016-03-02 | 2016-06-29 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon-coated lithium vanadate serving as negative electrode material of lithium ion battery |
| CN111033858A (en) * | 2017-08-30 | 2020-04-17 | 株式会社村田制作所 | Co-fired forming all-solid-state battery |
| CN111033858B (en) * | 2017-08-30 | 2023-06-16 | 株式会社村田制作所 | Co-fired all-solid battery |
| CN110323433A (en) * | 2019-07-10 | 2019-10-11 | 银隆新能源股份有限公司 | A kind of lithium titanate composite material and preparation method thereof, lithium ion battery and preparation method thereof |
| CN110323433B (en) * | 2019-07-10 | 2022-12-20 | 银隆新能源股份有限公司 | Lithium titanate composite material and preparation method thereof, lithium ion battery and preparation method thereof |
| CN111969189A (en) * | 2020-08-21 | 2020-11-20 | 贵州梅岭电源有限公司 | Lithium ion battery composite negative electrode material and preparation method thereof |
| CN111969189B (en) * | 2020-08-21 | 2021-10-26 | 贵州梅岭电源有限公司 | Lithium ion battery composite negative electrode material and preparation method thereof |
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