CN104051694A - Lithium polyoxometallate composite diaphragm for lithium battery - Google Patents
Lithium polyoxometallate composite diaphragm for lithium battery Download PDFInfo
- Publication number
- CN104051694A CN104051694A CN201410269455.3A CN201410269455A CN104051694A CN 104051694 A CN104051694 A CN 104051694A CN 201410269455 A CN201410269455 A CN 201410269455A CN 104051694 A CN104051694 A CN 104051694A
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- CN
- China
- Prior art keywords
- lithium salts
- acid lithium
- sio
- polyoxometallic acid
- composite diaphragm
- Prior art date
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Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims description 77
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 67
- 239000000843 powder Substances 0.000 claims description 53
- 229910003002 lithium salt Inorganic materials 0.000 claims description 48
- 159000000002 lithium salts Chemical class 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 230000004888 barrier function Effects 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000006424 Flood reaction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Separators (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a lithium polyoxometallate composite diaphragm for a lithium battery and a preparation method of the diaphragm. The composite diaphragm comprises a PVDF-HFP copolymer, SiO2 and lithium polyoxometallate, wherein the lithium polyoxometallate has a three-dimensional skeleton structure, and lithium ions are combined with anions of lithium polyoxometallate; in the battery charging/discharging process, the lithium ions of the lithium polyoxometallate can be continuously exchanged with the lithium ions in electrolyte, the combination of the diaphragm material with the lithium ions in the electrolyte is realized, the internal resistance of the battery is reduced, and the rate characteristic of the battery is improved.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to composite diaphragm and preparation method thereof for a kind of lithium battery, more specifically, the present invention relates to SiO
2composite diaphragm of carrier loaded polyoxometallic acid lithium salts and preparation method thereof.
Background technology
Lithium battery is because energy density is high, and the advantage such as have extended cycle life is used widely on market.Barrier film, as the vitals of lithium battery, plays vital effect.Diaphragm material itself is insulator, rises and separate positive/negative plate in battery, prevents the effect of internal short-circuit, and micropore sees through electrolyte simultaneously, guarantees that ionic conduction forms current circuit.In actual production, the conventional barrier film material of lithium battery is polyethylene film (PE), polypropylene film (PP) or three layers of laminated film (PP/PE/PP).Traditional lithium battery diaphragm material cannot be compatible with lithium ion, lithium ion can only reach the object of transmitting between both positive and negative polarity through barrier film micropore in charge and discharge process, certainly will affect the transmission rate of lithium ion, especially, in high current charge-discharge, affect the multiplying power property of battery.
Separately have patent announcement number for CN102529247A, the day for announcing is 2012.7.4, disclose a kind of inorganic/organic composite polypropylene non-woven fabric base lithium battery diaphragm and preparation method thereof.Described inorganic/organic composite porous lithium battery diaphragm, consists of substrate layer and the inorganic/organic composite porous rete that is arranged on substrate layer surface, and described substrate layer is polypropylene non-woven fabric; Described inorganic/organic composite porous rete is the Kynoar-hexafluoropropylene copolymer that contains inorganic nano-particle and hydrophilizing agent, described inorganic nano-particle is Nano particles of silicon dioxide or coupling agent modified Nano particles of silicon dioxide, foregoing invention is inorganic/organic composite polypropylene non-woven fabric base lithium battery diaphragm when guaranteeing high ionic conductivity, excellent electrochemical performance, high mechanical properties and low heat shrinkage, reduce the production cost of lithium battery diaphragm.Barrier film material described in it, only can play the effect that intercepts electronics, cannot realize with the lithium ion in electrolyte and combining, and its diversion sub-feature will inevitably be affected.
Summary of the invention
The present invention is directed to the above problem facing, polyoxometallic acid lithium salts composite diaphragm for a kind of lithium battery is provided, its principle is in charging and discharging lithium battery process, the lithium ion of polyoxometallic acid lithium salts can be constantly and in electrolyte lithium ion exchange, realize barrier film material and combined with the lithium ion in electrolyte, when playing the effect that intercepts electronics, guaranteed again its ion guide passband, reduce the internal resistance of cell, promoted the multiplying power property of battery.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A polyoxometallic acid lithium salts composite diaphragm for lithium battery, is characterized in that: described composite diaphragm comprises PVDF-HFP copolymer, SiO
2with polyoxometallic acid lithium salts.
Described polyoxometallic acid lithium salts is Li
3xY
12o
40, Li
4xY
12o
40, X refers in P, two kinds of elements of Si any one; Y refers in Mo, two kinds of elements of W any one.
A preparation method for polyoxometallic acid lithium salts composite diaphragm for lithium battery, is characterized in that: comprise the following steps:
A. by SiO
2powder leaches after dipping in the absolute methanol of polyoxometallic acid lithium salts or ethanol solution, dry, obtains polyoxometallic acid lithium salts-SiO
2complex carrier powder;
B. PVDF-HFP copolymer is stirred in acetone, obtain the solution of thickness;
C. according to PVDF-HFP copolymer and polyoxometallic acid lithium salts-SiO
2complex carrier powder is pressed the mass ratio of 10:1-5, by polyoxometallic acid lithium salts-SiO
2complex carrier powder adds in the solution of step B, stirs, and extrudes, stretches, is dried into the composite diaphragm that thickness is 10-40um after adding absolute ethyl alcohol to stir again.
Before described steps A, also comprise SiO
2processing, described processing is: by SiO
2powder salt acid soak, cleans with deionized water, then dry.
SiO
2powder is used salt acid soak 3 hours, cleans 300-1000 ℃ of dry 2-10 hour with deionized water.
Before described steps A, also comprise that the processing to polyoxometallic acid lithium salts, described processing are that 40-90 ℃ of polyoxometallic acid lithium salts dried to 1-10 hour.
The time of flooding in described steps A is 6-24 hour, and described is dry, is first at 60 ℃-200 ℃, to dry 1-10 hour, then at 300-600 ℃ of baking 2-10 hour.
Stirring in described step B is that PVDF-HFP copolymer stirs 1 hour at 50 ℃ of constant temperature.
By polyoxometallic acid lithium salts-SiO
2complex carrier powder adds in the solution of step B, stirs 4-24 hour, more dropwise adds absolute ethyl alcohol and stirring 2-30 minute.
The present invention has the following advantages:
1, polyoxometallic acid lithium salts composite diaphragm for lithium battery of the present invention, comprises PVDF-HFP copolymer, SiO
2with polyoxometallic acid lithium salts, polyoxometallic acid lithium salts has three-dimensional framework structure, lithium ion and polyoxometallic acid lithium salts anion binding, in battery charge and discharge process, the lithium ion of polyoxometallic acid lithium salts can be constantly and in electrolyte lithium ion exchange, realized barrier film material and combined with the lithium ion in electrolyte, when playing the effect that intercepts electronics, guarantee again its ion guide passband, reduced the internal resistance of cell, promoted the multiplying power property of battery.
2, polyoxometallic acid lithium salts of the present invention is Li
3xY
12o
40, Li
4xY
12o
40, X refers in P, two kinds of elements of Si any one; Y refers in Mo, two kinds of elements of W any one, and selected polyoxometallic acid lithium salts raw material is easy to get, Stability Analysis of Structures, and lithium ion is stable transfer therein.
3, preparation method of the present invention is at SiO
2space in load have polyoxometallic acid lithium salts, and mix PVDF-HFP copolymer and make, by this technique, polyoxometallic acid lithium salts steady load is to SiO
2space in, pass through SiO
2with the effect of PVDF-HFP, make polyoxometallic acid lithium salts steady load on barrier film material, become a part for barrier film material.
4, the present invention comprises SiO
2processing, by the object of salt acid soak, be to wash SiO
2metal impurities in powder, then be to clean SiO by the object of washed with de-ionized water
2the hydrochloric acid of middle remnants and other water-solubility impurity.
5, salt acid soak 3 hours in the present invention, is to make hydrochloric acid by SiO
2metal impurities in powder thoroughly react away; The setting of baking temperature and time is for guaranteeing SiO
2powder is thoroughly dried, and makes wherein not water content.
6, the processing of polyoxometallic acid lithium salts in the present invention, described processing is that 40-90 ℃ of polyoxometallic acid lithium salts dried to 1-10 hour, is for guaranteeing polyoxometallate finish-drying.
7, by SiO
2the time setting that powder is immersed in polyoxometallic acid lithium salt solution is for guaranteeing that polyoxometallic acid lithium salts enters SiO as far as possible
2in the space of powder, the setting of drying mode and temperature is for guaranteeing the finish-drying of complex carrier powder.
8, the PVDF-HFP copolymer whipping temp in the present invention and the setting of time are because the film forming under this temperature and time has more good aperture and ion transmission.
9, polyoxometallic acid lithium salts-SiO in the present invention
2complex carrier powder adds in the solution of step B, stirs 4-24 hour, is to be fully combined with PVDF-HFP, and be evenly distributed on the skeleton of barrier film base material for assurance complex carrier powder.
Embodiment
Embodiment 1
Its preparation method is:
1, polyoxometallic acid lithium salts-SiO
2the preparation of complex carrier
By SiO
2powder is at Li
3pMo
12o
40in absolute methanol solution, flood after 12 hours and leach, 100 ℃-120 ℃ are dried 2-3 hour, and 500 ℃ are toasted 3 hours, obtain Li
3pMo
12o
40-SiO
2complex carrier powder.
2, the preparation of composite diaphragm
By PVDF-HFP(Kynoar) copolymer stirs in acetone, obtains the solution of thickness, according to PVDF-HFP copolymer and Li
3pMo
12o
40-SiO
2complex carrier powder adds Li by the mass ratio of 10:2
3pMo
12o
40-SiO
2complex carrier powder stirs again, then adds absolute ethyl alcohol and stirring, finally extrudes, stretches, is dried into the film of 10-40um thickness.
The composite diaphragm of the present embodiment is tested for battery, and battery used is:
Anodal: active substance ferrous lithium phosphate content 93%, conductive carbon black content 3%, binding agent PVDF 4%, 16um thickness aluminum foil current collector, pole piece thickness 145um after colding pressing.
Negative pole: active material content of graphite 93%, conductive carbon black content 3%, binding agent PVDF4%, 15um thickness Copper Foil collector, pole piece thickness 100um after colding pressing.
Battery design capacity 20Ah
Detection method:
The multiplying power property that detects battery with Arbin BT2000 tester, idiographic flow is:
1, under normal temperature, with 1C electric current, by the first constant current of battery, constant voltage charge is to 3.65V again, and charging is 0.2A by electric current;
2, under normal temperature static 5 minutes, with 1C electric current by battery constant-current discharge to 2.5V, read the 1C discharge capacity of battery.
3, under normal temperature, with 1C electric current, by the first constant current of battery, constant voltage charge is to 3.65V again, and charging is 0.2A by electric current;
4, with 3C electric current by battery constant-current discharge to 2.5V, read the 3C discharge capacity of battery.
5, under normal temperature, with 1C electric current, by the first constant current of battery, constant voltage charge is to 3.65V again, and charging is 0.2A by electric current;
6, with 5C electric current by battery constant-current discharge to 2.5V, read the 5C discharge capacity of battery.
7, under normal temperature, with 1C electric current, by the first constant current of battery, constant voltage charge is to 3.65V again, and charging is 0.2A by electric current;
8, with 7C electric current by battery constant-current discharge to 2.5V, read the 7C discharge capacity of battery.
9., with 1C electric current, by the first constant current of battery, constant voltage charge is to 3.65V again under normal temperature, charging is 0.2A by electric current;
10, with 10C electric current by battery constant-current discharge to 2.5V, read the 10C discharge capacity of battery.
Embodiment 2
Preparation method is:
1, polyoxometallic acid lithium salts-SiO
2the preparation of complex carrier
SiO
2powder is used salt acid soak 3 hours, with deionized water, cleans, and 300 ℃ are toasted 10 hours.Phosphotungstic acid lithium Li
3pW
12o
40dry 1 hour for 90 ℃.SiO
2powder is at Li
3pW
12o
40in absolute methanol solution, flood after 6 hours and leach, 60 ℃ are dried 10 hours, and 300 ℃ are toasted 10 hours, obtain Li
3pW
12o
40-SiO
2complex carrier powder.
2, the preparation of composite diaphragm
PVDF-HFP copolymer 50 ℃ of constant temperature in acetone are stirred 1 hour, obtain the solution of thickness, according to PVDF-HFP copolymer and Li
3pW
12o
40-SiO
2complex carrier powder adds Li by the mass ratio of 10:3
3pW
12o
40-SiO
2complex carrier powder stirs 4 hours again, dropwise adds absolute ethyl alcohol and stirring 30 minutes, after extrude, stretch, be dried into the film of 10um thickness.
The composite diaphragm of the present embodiment is tested for battery, with embodiment 1.
Embodiment 3
Preparation method is:
1, polyoxometallic acid lithium salts-SiO
2the preparation of complex carrier
SiO
2powder is used salt acid soak 3 hours, with deionized water, cleans, and 600 ℃ are toasted 2 hours.Silicotungstate lithium Li
4siW
12o
40dry 10 hours for 40 ℃.SiO
2powder is at Li
4siW
12o
40in absolute methanol solution, flood after 24 hours and leach, 200 ℃ are dried 1 hour, and 600 ℃ are toasted 2 hours, obtain Li
4siW
12o
40-SiO
2complex carrier powder.
2, the preparation of composite diaphragm
PVDF-HFP copolymer 50 ℃ of constant temperature in acetone are stirred 1 hour, obtain the solution of thickness, according to PVDF-HFP copolymer and Li
4siW
12o
40-SiO
2complex carrier powder adds Li by the mass ratio of 10:5
4siW
12o
40-SiO
2complex carrier powder stirs 24 hours again, dropwise adds absolute ethyl alcohol and stirring 2 minutes, after extrude, stretch, be dried into the film of 40um thickness.
The composite diaphragm of the present embodiment is tested for battery, with embodiment 1.
Embodiment 4
Preparation method is:
1, polyoxometallic acid lithium salts-SiO
2the preparation of complex carrier
SiO
2powder is used salt acid soak 3 hours, with deionized water, cleans, and 400 ℃ are toasted 8 hours.Silicomolybdic acid lithium Li
4siMo
12o
40dry 3 hours for 80 ℃.SiO
2powder is at Li
4siMo
12o
40in absolute methanol solution, flood after 18 hours and leach, 120 ℃ are dried 5 hours, and 400 ℃ are toasted 4 hours, obtain Li
4siMo
12o
40-SiO
2complex carrier powder.
2, the preparation of composite diaphragm
PVDF-HFP copolymer 50 ℃ of constant temperature in acetone are stirred 1 hour, obtain the solution of thickness, according to PVDF-HFP copolymer and Li
4siMo
12o
40-SiO
2complex carrier powder adds Li by the mass ratio of 10:3.5
4siMo
12o
40-SiO
2complex carrier powder stirs 10 hours again, dropwise adds absolute ethyl alcohol and stirring 10 minutes, after extrude, stretch, be dried into the film of 30um thickness.
The composite diaphragm of the present embodiment is tested for battery, with embodiment 1.
Embodiment 5
Preparation method is:
1, polyoxometallic acid lithium salts-SiO
2the preparation of complex carrier
SiO
2powder is used salt acid soak 3 hours, with deionized water, cleans, and 400 ℃ are toasted 8 hours.Polyoxometallic acid lithium salts changes silicomolybdic acid lithium Li into
4siMo
12o
40with phosphomolybdic acid lithium Li
3pMo
12o
40the mixture of 1:1, dries 80 ℃, the mixture of two kinds of polyoxometallates 3 hours.SiO
2powder floods after 18 hours and leaches in the absolute methanol solution of polyoxometallate, and 120 ℃ are dried 5 hours, and 400 ℃ are toasted 4 hours, obtain Li
4siMo
12o
40-Li
3pMo
12o
40-SiO
2complex carrier powder.
2, the preparation of composite diaphragm
PVDF-HFP copolymer 50 ℃ of constant temperature in acetone are stirred 1 hour, obtain the solution of thickness, according to PVDF-HFP copolymer and Li
4siMo
12o
40-Li
3pMo
12o
40-siO
2complex carrier powder adds Li by the mass ratio of 10:3.5
4siMo
12o
40-Li
3pMo
12o
40-SiO
2complex carrier powder stirs 10 hours again, dropwise adds absolute ethyl alcohol and stirring 10 minutes, after extrude, stretch, be dried into the film of 30um thickness.
Embodiment 6
Preparation method is:
1, polyoxometallic acid lithium salts-SiO
2the preparation of complex carrier
SiO
2powder is used salt acid soak 3 hours, with deionized water, cleans, and 400 ℃ are toasted 8 hours.Polyoxometallic acid lithium salts changes silicomolybdic acid lithium Li into
4siW
12o
40with phosphomolybdic acid lithium Li
3pW
12o
40the mixture of 1:1, dries 80 ℃, the mixture of two kinds of polyoxometallates 3 hours.SiO
2powder floods after 18 hours and leaches in the absolute methanol solution of polyoxometallate, and 120 ℃ are dried 5 hours, and 400 ℃ are toasted 4 hours, obtain Li
4siW
12o
40-Li
3pW
12o
40-SiO
2complex carrier powder.
2, the preparation of composite diaphragm
PVDF-HFP copolymer 50 ℃ of constant temperature in acetone are stirred 1 hour, obtain the solution of thickness, according to PVDF-HFP copolymer and Li
4siMo
12o
40-Li
3pMo
12o
40-SiO
2complex carrier powder adds Li by the mass ratio of 10:3.5
4siW
12o
40-Li
3pW
12o
40-SiO
2complex carrier powder stirs 10 hours again, dropwise adds absolute ethyl alcohol and stirring 10 minutes, after extrude, stretch, be dried into the film of 30um thickness.
Comparative example 1
Operating procedure, with embodiment 1, just adopts without the SiO that crosses polyoxometallic acid lithium salts dipping
2make carrier, PVDF-HFP copolymer and SiO
2the mass ratio of support powder changes 10:3.5 into
Comparative example 2
Operating procedure, with embodiment 1, does not just adopt SiO
2make carrier, PVDF-HFP copolymer directly and Li
3pMo
12o
40it is compound that powder is pressed the mass ratio of 10:2.
Table 1 is the physical and chemical parameter contrast table of each embodiment and comparative example gained barrier film:
Table 2 is the AC internal Resistance contrast table that each embodiment and comparative example gained barrier film are made battery:
Table 3 is the large multiplying power discharging contrast table that each embodiment and comparative example gained barrier film are made battery:
From the physical and chemical parameter of table 1 to recently, barrier film without polyoxometallic acid lithium salts is larger than membrane pore size and porosity containing polyoxometallic acid lithium salts, AC internal Resistance from table 2, diaphragm cell internal resistance containing polyoxometallic acid lithium salts is not little than the barrier film internal resistance that does not contain polyoxometallic acid lithium salts, and the contrast of the low temperature of table 3 is found out, with the obvious advantage containing the large high rate performance of diaphragm cell of polyoxometallic acid lithium salts.Comparative example 2 is owing to there is no SiO
2make carrier, large rate capability has been less than SiO
2carrier, it is former because there is no SiO
2carrier, polyoxometallic acid lithium salts cannot be well compound with PVDF-HFP.
Claims (9)
1. a polyoxometallic acid lithium salts composite diaphragm for lithium battery, is characterized in that: described composite diaphragm comprises PVDF-HFP copolymer, SiO
2with polyoxometallic acid lithium salts.
2. polyoxometallic acid lithium salts composite diaphragm for a kind of lithium battery according to claim 1, is characterized in that: described polyoxometallic acid lithium salts is Li
3xY
12o
40, Li
4xY
12o
40, X refers in P, two kinds of elements of Si any one; Y refers in Mo, two kinds of elements of W any one.
3. the preparation method of polyoxometallic acid lithium salts composite diaphragm for lithium battery according to claim 1, is characterized in that: comprise the following steps:
A. by SiO
2powder leaches after dipping in the absolute methanol of polyoxometallic acid lithium salts or ethanol solution, dry, obtains polyoxometallic acid lithium salts-SiO
2complex carrier powder;
B. PVDF-HFP copolymer is stirred in acetone, obtain the solution of thickness;
C. according to PVDF-HFP copolymer and polyoxometallic acid lithium salts-SiO
2complex carrier powder is pressed the mass ratio of 10:1-5, by polyoxometallic acid lithium salts-SiO
2complex carrier powder adds in the solution of step B, stirs, and extrudes, stretches, is dried into the composite diaphragm that thickness is 10-40um after adding absolute ethyl alcohol to stir again.
4. the preparation method of polyoxometallic acid lithium salts composite diaphragm for lithium battery according to claim 3, is characterized in that:
Before described steps A, also comprise SiO
2processing, described processing is: by SiO
2powder salt acid soak, cleans with deionized water, then dry.
5. the preparation method of polyoxometallic acid lithium salts composite diaphragm for lithium battery according to claim 4, is characterized in that: SiO
2powder is used salt acid soak 3 hours, cleans 300-1000 ℃ of dry 2-10 hour with deionized water.
6. the preparation method of polyoxometallic acid lithium salts composite diaphragm for lithium battery according to claim 3, is characterized in that:
Before described steps A, also comprise that the processing to polyoxometallic acid lithium salts, described processing are that 40-90 ℃ of polyoxometallic acid lithium salts dried to 1-10 hour.
7. the preparation method of polyoxometallic acid lithium salts composite diaphragm for lithium battery according to claim 3, is characterized in that:
The time of flooding in described steps A is 6-24 hour, and described is dry, is first at 60 ℃-200 ℃, to dry 1-10 hour, then at 300-600 ℃ of baking 2-10 hour.
8. the preparation method of polyoxometallic acid lithium salts composite diaphragm for lithium battery according to claim 3, is characterized in that:
Stirring in described step B is that PVDF-HFP copolymer stirs 1 hour at 50 ℃ of constant temperature.
9. the preparation method of polyoxometallic acid lithium salts composite diaphragm for lithium battery according to claim 3, is characterized in that:
By polyoxometallic acid lithium salts-SiO
2complex carrier powder adds in the solution of step B, stirs 4-24 hour, more dropwise adds absolute ethyl alcohol and stirring 2-30 minute.
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| CN105977430A (en) * | 2016-06-18 | 2016-09-28 | 清华大学 | Polyoxometallic acid lithium salt ceramic membrane for lithium-ion battery |
| CN109817865A (en) * | 2018-12-19 | 2019-05-28 | 长沙新材料产业研究院有限公司 | A kind of composite diaphragm and preparation method thereof |
| CN117374515A (en) * | 2023-12-06 | 2024-01-09 | 天津力神电池股份有限公司 | Separator with lithium ion capacity compensation function, preparation method thereof and battery |
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| CN117374515B (en) * | 2023-12-06 | 2024-04-19 | 天津力神电池股份有限公司 | Separator with lithium ion capacity compensation function, preparation method thereof and battery |
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|---|---|
| CN104051694B (en) | 2016-06-01 |
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