CN104051694B - The preparation method of a kind of lithium cell polyoxometallic acid lithium salt composite diaphragm - Google Patents
The preparation method of a kind of lithium cell polyoxometallic acid lithium salt composite diaphragm Download PDFInfo
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- CN104051694B CN104051694B CN201410269455.3A CN201410269455A CN104051694B CN 104051694 B CN104051694 B CN 104051694B CN 201410269455 A CN201410269455 A CN 201410269455A CN 104051694 B CN104051694 B CN 104051694B
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- 239000002253 acid Substances 0.000 title claims abstract description 80
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 50
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 67
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 65
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 65
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 65
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 65
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 31
- 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
- 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
- 238000001035 drying Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 claims description 2
- 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
- 230000004888 barrier function Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 10
- 239000008151 electrolyte solution Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 18
- 239000004743 Polypropylene Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229910020881 PMo12O40 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910020628 SiW12O40 Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000013543 active substance Substances 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
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 229910052710 silicon Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007822 coupling agent Substances 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
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000573 polyethylene 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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Silicon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of lithium cell polyoxometallic acid lithium salt composite diaphragm and its preparation method, and composite diaphragm comprises PVDF-HFP multipolymer, SiO2With polyoxometallic acid lithium salt, polyoxometallic acid lithium salt has three dimensional skeletal structure, lithium ion is combined with polyoxometallic acid lithium salt anionic, in battery charge and discharge process, the lithium ion of polyoxometallic acid lithium salt can exchange by lithium ion constantly and in electrolytic solution, achieve barrier film material to combine with the lithium ion in electrolytic solution, reduce the internal resistance of cell, improve the multiplying power property of battery.
Description
Technical field
The invention belongs to technical field of lithium ion, it is specifically related to a kind of lithium cell composite diaphragm and its preparation method, in particular, it relates to SiO2The composite diaphragm of carrier loaded polyoxometallic acid lithium salt and its preparation method.
Background technology
Lithium cell is due to energy density height, and the advantage such as have extended cycle life, and is commercially used widely. Barrier film, as the important parts of lithium cell, plays most important effect. Diaphragm material itself is isolator, rises in the battery and separates positive/negative plate, prevents the effect of internal short-circuit, and micropore is through electrolytic solution simultaneously, ensures that ionic conduction forms current circuit. In actual production, the conventional barrier film material of lithium cell 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 transmission positive and negative electrode in charge and discharge process through diaphragm micro-hole, the transfer rate of lithium ion certainly will be affected, especially when high current charge-discharge, affect the multiplying power property of battery.
Separately having patent announcement number to be 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 its preparation method. Described inorganic/organic composite porous lithium battery diaphragm, is made up of substrate layer and the inorganic/organic composite porous rete being arranged on substrate layer surface, and described substrate layer is polypropylene non-woven fabric; Described inorganic/organic composite porous rete is the polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer containing 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 while ensureing high ionic conductivity, excellent electrochemical performance, high mechanical strength and low heat shrinkage, reduce the production cost of lithium battery diaphragm. Barrier film material described in it, only can play the effect intercepting electronics, cannot realize combining with the lithium ion in electrolytic solution, and it leads ion characteristic will inevitably be affected.
Summary of the invention
The present invention is directed to above problems faced, provide the preparation method of a kind of lithium cell polyoxometallic acid lithium salt composite diaphragm, its principle is in charging and discharging lithium battery process, the lithium ion of polyoxometallic acid lithium salt can exchange by lithium ion constantly and in electrolytic solution, achieve barrier film material to combine with the lithium ion in electrolytic solution, while playing the effect intercepting electronics, in turn ensure that its ion on-state rate, reduce the internal resistance of cell, improve 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 kind of lithium cell polyoxometallic acid lithium salt composite diaphragm, it is characterised in that: described composite diaphragm comprises PVDF-HFP multipolymer, SiO2With polyoxometallic acid lithium salt.
Described polyoxometallic acid lithium salt is Li3XY12O40, Li4XY12O40, X refers in P, Si two kinds of elements any one; Y refers in Mo, W two kinds of elements any one.
The preparation method of a kind of lithium cell polyoxometallic acid lithium salt composite diaphragm, it is characterised in that: comprise the following steps:
A. by SiO2Powder is filtered out after flooding in the anhydrous methanol or ethanol solution of polyoxometallic acid lithium salt, dry, obtains polyoxometallic acid lithium salt-SiO2Complex carrier powder;
B. PVDF-HFP multipolymer is stirred in acetone, obtain sticky thick solution;
C. according to PVDF-HFP multipolymer and polyoxometallic acid lithium salt-SiO2Complex carrier powder presses the mass ratio of 10:1 5, by polyoxometallic acid lithium salt-SiO2Complex carrier powder adds in the solution of step B, stirs, and adds after dehydrated alcohol stirs again and extrudes, stretches, is dried into the composite diaphragm that thickness is 10-40um.
Also comprise SiO before described steps A2Process, described process is: by SiO2Powder salt acid soak, cleans with deionized water, then dry.
SiO2Powder salt acid soak 3 hours, cleans with deionized water, and 300-1000 DEG C dry 2-10 hour.
Also comprising the process to polyoxometallic acid lithium salt before described steps A, described process is dried 1-10 hour by polyoxometallic acid lithium salt 40-90 DEG C.
In described steps A, the time of dipping is 6-24 hour, described drying, is first dry 1-10 hour at 60 DEG C-200 DEG C, then toasts 2-10 hour at 300-600 DEG C.
Stirring in described step B is, PVDF-HFP multipolymer stirs 1 hour at 50 DEG C of constant temperature.
By polyoxometallic acid lithium salt-SiO2Complex 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, the lithium cell of the present invention polyoxometallic acid lithium salt composite diaphragm, comprises PVDF-HFP multipolymer, SiO2With polyoxometallic acid lithium salt, polyoxometallic acid lithium salt has three dimensional skeletal structure, lithium ion is combined with polyoxometallic acid lithium salt anionic, in battery charge and discharge process, the lithium ion of polyoxometallic acid lithium salt can exchange by lithium ion constantly and in electrolytic solution, it is achieved that barrier film material combines with the lithium ion in electrolytic solution, while playing the effect intercepting electronics, in turn ensure that its ion on-state rate, reduce the internal resistance of cell, improve the multiplying power property of battery.
2, the polyoxometallic acid lithium salt of the present invention is Li3XY12O40, Li4XY12O40, X refers in P, Si two kinds of elements any one; Y refers in Mo, W two kinds of elements any one, and selected polyoxometallic acid lithium salt raw material is easy to get, Stability Analysis of Structures, and lithium ion can stable transfer wherein.
3, the preparation method of the present invention is at SiO2Space in load have polyoxometallic acid lithium salt, and mix PVDF-HFP multipolymer and make, by this technique, polyoxometallic acid lithium salt steady load is to SiO2Space in, pass through SiO2With the effect of PVDF-HFP, make polyoxometallic acid lithium salt steady load to, in barrier film material, becoming a part for barrier film material.
4, the present invention comprises SiO2Process, be wash SiO by the object of salt acid soak2Metallic impurity in powder, then be clean SiO by the object of washed with de-ionized water2The hydrochloric acid of middle remnants and other water-soluble impurity.
5, salt acid soak 3 hours in the present invention, are to make hydrochloric acid by SiO2Metallic impurity in powder thoroughly react away; The setting of drying temperature and time is for ensureing SiO2Powder is thoroughly dried so that it is in not water content.
6, the process of polyoxometallic acid lithium salt in the present invention, described process is dried 1-10 hour by polyoxometallic acid lithium salt 40-90 DEG C, is be ensure polyoxometallate finish-drying.
7, by SiO2The time setting that powder is immersed in polyoxometallic acid lithium salt solution is for ensureing that polyoxometallic acid lithium salt enters SiO as far as possible2In the space of powder, the setting of drying mode and temperature is the finish-drying for ensureing complex carrier powder.
8, the PVDF-HFP multipolymer whipping temp in the present invention and the setting of time are because the film formed under this temperature and time has more good aperture and ion transmission.
9, polyoxometallic acid lithium salt-SiO in the present invention2Complex carrier powder adds in the solution of step B, stirs 4-24 hour, is for ensureing that complex carrier powder is fully combined with PVDF-HFP, and is evenly distributed on the skeleton of barrier film base material.
Embodiment
Embodiment 1
Its preparation method is:
1, polyoxometallic acid lithium salt-SiO2The preparation of complex carrier
By SiO2Powder is at Li3PMo12O40Filtering out after flooding 12 hours in absolute methanol solution, 100 DEG C-120 DEG C are dried 2-3 hour, and 500 DEG C are toasted 3 hours, obtain Li3PMo12O40-SiO2Complex carrier powder.
2, the preparation of composite diaphragm
By PVDF-HFP(polyvinylidene difluoride (PVDF)) multipolymer stirs in acetone, obtains sticky thick solution, according to PVDF-HFP multipolymer and Li3PMo12O40-SiO2Complex carrier powder adds Li by the mass ratio of 10:23PMo12O40-SiO2Complex carrier powder stirs again, then adds absolute ethyl alcohol and stirring, finally extrude, stretches, is dried into the film of 10-40um thickness.
Being used in battery to test by the composite diaphragm of the present embodiment, battery used is:
Positive pole: active substance ferrous lithium phosphate content 93%, conductive carbon black content 3%, binding agent PVDF4%, 16um thickness aluminum foil current collector, pole piece thickness 145um after colding pressing.
Negative pole: active substance content of graphite 93%, conductive carbon black content 3%, binding agent PVDF4%, 15um thickness copper foil current collector, pole piece thickness 100um after colding pressing.
Battery design capacity 20Ah
Detection method:
Detect the multiplying power property of battery with ArbinBT2000 tester, idiographic flow is:
1, under normal temperature with 1C electric current by first for battery constant current again constant voltage charge to 3.65V, charge by electric current be 0.2A;
2, under normal temperature static 5 minutes, with 1C electric current by battery constant-current discharge to 2.5V, the 1C loading capacity of battery is read.
3, under normal temperature with 1C electric current by first for battery constant current again constant voltage charge to 3.65V, charge by electric current be 0.2A;
4, with 3C electric current by battery constant-current discharge to 2.5V, read the 3C loading capacity of battery.
5, under normal temperature with 1C electric current by first for battery constant current again constant voltage charge to 3.65V, charge by electric current be 0.2A;
6, with 5C electric current by battery constant-current discharge to 2.5V, read the 5C loading capacity of battery.
7, under normal temperature with 1C electric current by first for battery constant current again constant voltage charge to 3.65V, charge by electric current be 0.2A;
8, with 7C electric current by battery constant-current discharge to 2.5V, read the 7C loading capacity of battery.
9., under normal temperature with 1C electric current by first for battery constant current again constant voltage charge to 3.65V, charge by electric current be 0.2A;
10, with 10C electric current by battery constant-current discharge to 2.5V, read the 10C loading capacity of battery.
Embodiment 2
Preparation method is:
1, polyoxometallic acid lithium salt-SiO2The preparation of complex carrier
SiO2Powder salt acid soak 3 hours, cleans with deionized water, 300 DEG C of bakings 10 hours. Phospho-wolframic acid lithium Li3PW12O40Dry 1 hour for 90 DEG C. SiO2Powder is at Li3PW12O40Filtering out after flooding 6 hours in absolute methanol solution, 60 DEG C are dried 10 hours, and 300 DEG C are toasted 10 hours, obtain Li3PW12O40-SiO2Complex carrier powder.
2, the preparation of composite diaphragm
By PVDF-HFP multipolymer in acetone 50 DEG C of constant temperature stir 1 hour, obtain sticky thick solution, according to PVDF-HFP multipolymer and Li3PW12O40-SiO2Complex carrier powder adds Li by the mass ratio of 10:33PW12O40-SiO2Complex carrier powder stirs 4 hours again, dropwise adds absolute ethyl alcohol and stirring 30 minutes, after extrude, the film of the 10um thickness that stretches, is dried into.
The composite diaphragm of the present embodiment is used in battery to test, with embodiment 1.
Embodiment 3
Preparation method is:
1, polyoxometallic acid lithium salt-SiO2The preparation of complex carrier
SiO2Powder salt acid soak 3 hours, cleans with deionized water, 600 DEG C of bakings 2 hours. Silicotungstate lithium Li4SiW12O40Dry 10 hours for 40 DEG C. SiO2Powder is at Li4SiW12O40Filtering out after flooding 24 hours in absolute methanol solution, 200 DEG C are dried 1 hour, and 600 DEG C are toasted 2 hours, obtain Li4SiW12O40-SiO2Complex carrier powder.
2, the preparation of composite diaphragm
By PVDF-HFP multipolymer in acetone 50 DEG C of constant temperature stir 1 hour, obtain sticky thick solution, according to PVDF-HFP multipolymer and Li4SiW12O40-SiO2Complex carrier powder adds Li by the mass ratio of 10:54SiW12O40-SiO2Complex carrier powder stirs 24 hours again, dropwise adds absolute ethyl alcohol and stirring 2 minutes, after extrude, the film of the 40um thickness that stretches, is dried into.
The composite diaphragm of the present embodiment is used in battery to test, with embodiment 1.
Embodiment 4
Preparation method is:
1, polyoxometallic acid lithium salt-SiO2The preparation of complex carrier
SiO2Powder salt acid soak 3 hours, cleans with deionized water, 400 DEG C of bakings 8 hours. Silicomolybdic acid lithium Li4SiMo12O40Dry 3 hours for 80 DEG C. SiO2Powder is at Li4SiMo12O40Filtering out after flooding 18 hours in absolute methanol solution, 120 DEG C are dried 5 hours, and 400 DEG C are toasted 4 hours, obtain Li4SiMo12O40-SiO2Complex carrier powder.
2, the preparation of composite diaphragm
By PVDF-HFP multipolymer in acetone 50 DEG C of constant temperature stir 1 hour, obtain sticky thick solution, according to PVDF-HFP multipolymer and Li4SiMo12O40-SiO2Complex carrier powder adds Li by the mass ratio of 10:3.54SiMo12O40-SiO2Complex carrier powder stirs 10 hours again, dropwise adds absolute ethyl alcohol and stirring 10 minutes, after extrude, the film of the 30um thickness that stretches, is dried into.
The composite diaphragm of the present embodiment is used in battery to test, with embodiment 1.
Embodiment 5
Preparation method is:
1, polyoxometallic acid lithium salt-SiO2The preparation of complex carrier
SiO2Powder salt acid soak 3 hours, cleans with deionized water, 400 DEG C of bakings 8 hours. Polyoxometallic acid lithium salt changes silicomolybdic acid lithium Li into4SiMo12O40With phospho-molybdic acid lithium Li3PMo12O40The mixture of 1:1, dries 80 DEG C, the mixture of two kinds of polyoxometallates 3 hours. SiO2Powder is filtered out after flooding 18 hours in the absolute methanol solution of polyoxometallate, and 120 DEG C are dried 5 hours, and 400 DEG C are toasted 4 hours, obtain Li4SiMo12O40-Li3PMo12O40-SiO2Complex carrier powder.
2, the preparation of composite diaphragm
By PVDF-HFP multipolymer in acetone 50 DEG C of constant temperature stir 1 hour, obtain sticky thick solution, according to PVDF-HFP multipolymer and Li4SiMo12O40-Li3PMo12O40-SiO2Complex carrier powder adds Li by the mass ratio of 10:3.54SiMo12O40-Li3PMo12O40-SiO2Complex carrier powder stirs 10 hours again, dropwise adds absolute ethyl alcohol and stirring 10 minutes, after extrude, the film of the 30um thickness that stretches, is dried into.
Embodiment 6
Preparation method is:
1, polyoxometallic acid lithium salt-SiO2The preparation of complex carrier
SiO2Powder salt acid soak 3 hours, cleans with deionized water, 400 DEG C of bakings 8 hours. Polyoxometallic acid lithium salt changes silicomolybdic acid lithium Li into4SiW12O40With phospho-molybdic acid lithium Li3PW12O40The mixture of 1:1, dries 80 DEG C, the mixture of two kinds of polyoxometallates 3 hours. SiO2Powder is filtered out after flooding 18 hours in the absolute methanol solution of polyoxometallate, and 120 DEG C are dried 5 hours, and 400 DEG C are toasted 4 hours, obtain Li4SiW12O40-Li3PW12O40-SiO2Complex carrier powder.
2, the preparation of composite diaphragm
By PVDF-HFP multipolymer in acetone 50 DEG C of constant temperature stir 1 hour, obtain sticky thick solution, according to PVDF-HFP multipolymer and Li4SiMo12O40-Li3PMo12O40-SiO2Complex carrier powder adds Li by the mass ratio of 10:3.54SiW12O40-Li3PW12O40-SiO2Complex carrier powder stirs 10 hours again, dropwise adds absolute ethyl alcohol and stirring 10 minutes, after extrude, the film of the 30um thickness that stretches, is dried into.
Comparative example 1
Operation steps, with embodiment 1, just adopts the SiO without polyoxometallic acid lithium salt dipping2Make carrier, PVDF-HFP multipolymer and SiO2The mass ratio of support powder changes 10:3.5 into
Comparative example 2
Operation steps, with embodiment 1, does not just adopt SiO2Making carrier, PVDF-HFP multipolymer is directly and Li3PMo12O40Powder compares compound by the quality 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 battery made by each embodiment and comparative example gained barrier film:
Table 3 is the big multiplying power discharging contrast table that battery made by each embodiment and comparative example gained barrier film:
Contrast from the physical and chemical parameter of table 1, barrier film without polyoxometallic acid lithium salt is bigger than membrane pore size and the porosity containing polyoxometallic acid lithium salt, from the AC internal Resistance of table 2, diaphragm cell internal resistance containing polyoxometallic acid lithium salt is less than the barrier film internal resistance not containing polyoxometallic acid lithium salt, and table 3 low temperature contrast find out, the big high rate performance of diaphragm cell containing polyoxometallic acid lithium salt is with the obvious advantage. Comparative example 2 is not owing to having SiO2Making carrier, big rate capability is less than SiO2Carrier, its reason is not for having SiO2Carrier, polyoxometallic acid lithium salt cannot compound good with PVDF-HFP.
Claims (7)
1. the lithium cell preparation method of polyoxometallic acid lithium salt composite diaphragm, it is characterised in that: comprise the following steps:
A. by SiO2Powder is filtered out after flooding in the anhydrous methanol or ethanol solution of polyoxometallic acid lithium salt, dry, obtains polyoxometallic acid lithium salt-SiO2Complex carrier powder;
B. PVDF-HFP multipolymer is stirred in acetone, obtain sticky thick solution;
C. according to PVDF-HFP multipolymer and polyoxometallic acid lithium salt-SiO2Complex carrier powder presses the mass ratio of 10:1 5, by polyoxometallic acid lithium salt-SiO2Complex carrier powder adds in the solution of step B, stirs, and adds after dehydrated alcohol stirs again and extrudes, stretches, is dried into the composite diaphragm that thickness is 10-40um.
2. the preparation method of lithium cell polyoxometallic acid lithium salt composite diaphragm according to claim 1, it is characterised in that:
Also comprise SiO before described steps A2Process, described process is: by SiO2Powder salt acid soak, cleans with deionized water, then dry.
3. the preparation method of lithium cell polyoxometallic acid lithium salt composite diaphragm according to claim 2, it is characterised in that: SiO2Powder salt acid soak 3 hours, cleans with deionized water, and 300-1000 DEG C dry 2-10 hour.
4. the preparation method of lithium cell polyoxometallic acid lithium salt composite diaphragm according to claim 1, it is characterised in that:
Also comprising the process to polyoxometallic acid lithium salt before described steps A, described process is dried 1-10 hour by polyoxometallic acid lithium salt 40-90 DEG C.
5. the preparation method of lithium cell polyoxometallic acid lithium salt composite diaphragm according to claim 1, it is characterised in that:
In described steps A, the time of dipping is 6-24 hour, described drying, is first dry 1-10 hour at 60 DEG C-200 DEG C, then toasts 2-10 hour at 300-600 DEG C.
6. the preparation method of lithium cell polyoxometallic acid lithium salt composite diaphragm according to claim 1, it is characterised in that:
Stirring in described step B is, PVDF-HFP multipolymer stirs 1 hour at 50 DEG C of constant temperature.
7. the preparation method of lithium cell polyoxometallic acid lithium salt composite diaphragm according to claim 1, it is characterised in that:
By polyoxometallic acid lithium salt-SiO2Complex 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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| CN109817865B (en) * | 2018-12-19 | 2022-10-21 | 航天科工(长沙)新材料研究院有限公司 | Composite diaphragm and preparation method thereof |
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