CN104051693A - Polyoxometallic acid lithium ceramic diaphragm of lithium ion battery - Google Patents
Polyoxometallic acid lithium ceramic diaphragm of lithium ion battery Download PDFInfo
- Publication number
- CN104051693A CN104051693A CN201410268878.3A CN201410268878A CN104051693A CN 104051693 A CN104051693 A CN 104051693A CN 201410268878 A CN201410268878 A CN 201410268878A CN 104051693 A CN104051693 A CN 104051693A
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- China
- Prior art keywords
- acid lithium
- polyoxometallic acid
- lithium salts
- ceramic
- diaphragm
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Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 92
- 239000002253 acid Substances 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 58
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 22
- 229920000098 polyolefin Polymers 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 40
- 159000000002 lithium salts Chemical class 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002033 PVDF binder Substances 0.000 claims description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 15
- 229910004764 HSV900 Inorganic materials 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 2
- 238000007581 slurry coating method Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 description 32
- 239000000758 substrate Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 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 4
- 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 4
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 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
- 239000011889 copper foil Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 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
- H01M50/431—Inorganic material
-
- 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
Abstract
The invention discloses a polyoxometallic acid lithium ceramic diaphragm of a lithium ion battery. The surface of a polyolefin diaphragm base material is coated with Al2O3 composite ceramic powder containing polyoxometallic acid lithium, and as Li3XY12O40 and Li4XY12O40 respectively have a three-dimensional framework structure, lithium ions are combined with polyoxometallate anion, and in the charge/discharge process of a battery, lithium ions of polyoxometallate can be exchanged with lithium ions in electrolyte constantly, so that the security of the ceramic diaphragm is maintained, and the transmission velocity of lithium ions is improved.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of composite diaphragm for lithium ion battery and preparation method, more specifically, the present invention relates to the ceramic diaphragm of load polyoxometallic acid lithium salts in the hole of ceramic powders.
Background technology
Lithium ion battery is since commercialization, because it has that energy density is high, operating voltage is high, memory-less effect and the feature such as have extended cycle life be widely used as the power supply of various mobile devices.And very likely become the topmost power-supply system of energy storage and electric automobile field, still, along with the large-scale application of lithium ion battery, cell safety problem highlights day by day.
One of key factor that affects security of lithium-ion-power cell is exactly the fail safe of barrier film, for the barrier film of lithium ion battery, must possess good electrochemistry and thermal stability, and in repeated charge process, electrolyte is kept to height wettability.General polyolefin-based separator is mainly polyethylene (PE) microporous barrier and polypropylene (PP) microporous barrier at present, the fusing point of this two classes film is respectively 130 ℃ and 150 ℃ of left and right, therefore they easily shrink or melting at higher temperature, cause the direct contact between positive pole and negative pole, cause the generation of short circuit, thereby cause the generation of contingency, as battery explosion being caused by electric discharge etc.
Along with global energy shortage, environmental pollution, greenhouse effect aggravation, electric automobile is compared and traditional fuel vehicle, has zero discharge, pollution-free, as the development trend of following replacing fuel oil car, arises at the historic moment.Electrokinetic cell is the core of electric automobile, and barrier film is the bottleneck of electric automobile power battery development, and traditional barrier film is owing at high temperature easily shrinking and causing battery internal short-circuit, thereby has restricted stability and the security reliability of electric automobile.In recent years, from improving electrokinetic cell fail safe, set about, ceramic diaphragm has obtained very great development, this at conventional membrane surface coating one deck rigidity oxide (Al
2o
3, SiO
2deng) barrier film, can be when barrier film is met high temperature by the rigidity effect of oxide, supporting barrier film not shrink, and can improve to a certain extent the fail safe of electrokinetic cell.
But, existing Ceramic Composite barrier film most just simply by ceramic powder suspension in solvent or binder solution, any processing is not done on ceramic powders surface, due to adding of rigidity oxide, hindered the normal migration of lithium ion in barrier film, lithium-ion-conducting is poor, makes ceramic diaphragm battery not reach the electrical property of conventional membrane battery, has a strong impact on the application of ceramic diaphragm in electric automobile power battery.
Summary of the invention
The present invention has aimed to provide polyoxometallic acid lithium salts ceramic diaphragm and preparation method thereof for a kind of lithium ion battery, object is on base material, to apply the ceramic powders containing polyoxometallic acid lithium salts, the existence of ceramic powders can keep ceramic diaphragm fail safe, polyoxometallic acid lithium salts improves again the transmission rate of lithium ion, has met the double grading of fail safe and transfer rate.
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 ceramic diaphragm for lithium ion battery, comprises polyalkene diaphragm base material, it is characterized in that: the surface-coated of described polyalkene diaphragm base material is containing the Al of polyoxometallic acid lithium salts
2o
3composite ceramic powder.
Described polyoxometallic acid lithium salts is Li
3xY
12o
40or 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.
Described polyalkene diaphragm base material is the monofilm of polypropylene (PP), polyethylene (PE), or the trilamellar membrane being comprised of two kinds of materials.
A preparation method for polyoxometallic acid lithium salts ceramic diaphragm for lithium ion battery, is characterized in that: comprise the steps:
(1) Al
2o
3ceramic powders and the polyoxometallate in mass ratio ratio of 10:1 – 5 divide and get, and ceramic powders are immersed in the absolute methanol or ethanol solution of polyoxometallic acid lithium salts, then leach, dry, obtain polyoxometallic acid lithium salts-Al
2o
3composite ceramic powder;
(2) by Kynoar (PVDF, HSV900) and polyoxometallic acid lithium salts-Al
2o
3composite ceramic powder, adds in 1-METHYLPYRROLIDONE (NMP) and stirs, and is mixed into slurry;
(3) slurry step (2) being made is coated on the surface of polyalkene diaphragm base material, then dry forming.
Al in described step (1)
2o
3ceramic powders is immersed in the absolute methanol of polyoxometallic acid lithium salts or the time of ethanol solution is 4-24 hour.
Drying mode in described step (1) is: first 60-100 ℃ water bath method, then 80 ℃-160 ℃ are dried 3-4 hour, last 200-1000 ℃ of baking 3 hours.
In described step (3), slurry coating is 2um-10um to the surperficial thickness of polyalkene diaphragm base material.
Being dried in described step (3) is: the polyalkene diaphragm base material that is coated with slurry is dry through coating machine oven 75-95 ℃.
Kynoar (PVDF, HSV900) and polyoxometallic acid lithium salts-Al in described step (2)
2o
3the ratio of composite ceramic is 1:5-20.
The present invention has the following advantages:
1, lithium ion battery of the present invention is that surface-coated at polyalkene diaphragm base material has the Al containing polyoxometallic acid lithium salts with polyoxometallic acid lithium salts ceramic diaphragm
2o
3composite ceramic powder, due to Li
3xY
12o
40, Li
4xY
12o
40there is three-dimensional framework structure, lithium ion and polyoxometallate anion binding, in battery charge and discharge process, the lithium ion of polyoxometallate can be constantly and in electrolyte lithium ion exchange, both keep ceramic diaphragm fail safe, improved again the transmission rate of lithium ion.
2, polyoxometallic acid lithium salts of the present invention is Li
3xY
12o
40or 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, selected polyoxometallic acid lithium salts, and raw material is easy to get, Stability Analysis of Structures, lithium ion can freely transmit therein.
3, lithium ion battery of the present invention, with ceramic powders being immersed in the absolute methanol or ethanol solution of polyoxometallic acid lithium salts in the preparation method of polyoxometallic acid lithium salts ceramic diaphragm, then leaches, dry, obtains polyoxometallic acid lithium salts-Al
2o
3ceramic powders; Make polyoxometallate fully adulterate and enter in ceramic powders.
By Kynoar (PVDF, HSV900) and polyoxometallic acid lithium salts-Al
2o
3composite ceramic powder stirs in 1-METHYLPYRROLIDONE (NMP) by 1:10--20, is mixed into slurry; Kynoar (PVDF), as binding agent, can be bonded at ceramic powders in barrier film substrate, and the viscosity of selecting the ratio of 1:10-20 to be conducive to slurry is controlled, and is convenient to coating.
4, Al of the present invention
2o
3ceramic powders is immersed in the absolute methanol of polyoxometallic acid lithium salts or the time of ethanol solution is 4-24 hour, makes polyoxometallate fully adulterate and enter in ceramic powders.
5, the barrier film that prepared by the present invention through coating machine oven 75-95 ℃ dry, coating machine has more piece baking oven, is staged temperature, arrives from low to high lowly again, is conducive to the rapid draing of barrier film, can not produce again the barrier film deformation causing because of excess Temperature.
6, Kynoar of the present invention (PVDF, HSV900) and polyoxometallic acid lithium salts-Al
2o
3the ratio of composite ceramic is 1:10-20, and Kynoar (PVDF), as binding agent, can be bonded at ceramic powders in barrier film substrate, and the viscosity of selecting the ratio of 1:10-20 to be conducive to slurry is controlled, and is convenient to coating.
Embodiment
Embodiment 1
A polyoxometallic acid lithium salts ceramic diaphragm for lithium ion battery, comprises polyalkene diaphragm base material, and this ceramic diaphragm is in the surface-coated of polyalkene diaphragm base material, to contain the Al of polyoxometallic acid lithium salts
2o
3composite ceramic powder.
Described polyoxometallic acid lithium salts is Li
3xY
12o
40or 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.
Described polyalkene diaphragm base material is the monofilm of polypropylene (PP), polyethylene (PE), or the trilamellar membrane being comprised of two kinds of materials.
Its preparation method is: the preparation method of this polyoxometallic acid lithium salts ceramic diaphragm is at Al
2o
3load polyoxometallic acid lithium salts in the hole of ceramic powders, then the ceramic powders containing polyoxometallic acid lithium salts is coated on polyalkene diaphragm with coating machine, polyoxometallic acid lithium salts Al obtained
2o
3ceramic diaphragm.Concrete steps are as follows:
1, Li
3pMo
12o
40-Al
2o
3the preparation of composite ceramic powder
By Al
2o
3ceramic powders and phosphomolybdic acid lithium Li
3pMo
12o
40the ratio of 10:4.3 takes in mass ratio, by Al
2o
3ceramic powders is immersed in phosphomolybdic acid lithium Li
3pMo
12o
40in absolute methanol solution, after 14 hours, leach, 80 ℃ of water bath methods, after preliminarily dried, then 100 ℃-120 ℃ baking 3-4 hour, then 500 ℃ are toasted 3 hours, obtain Li
3pMo
12o
40-Al
2o
3composite ceramic powder.
2, the preparation of ceramic diaphragm
According to Kynoar (PVDF, HSV900) and Li
3pMo
12o
40-Al
2o
3the ratio of composite ceramic powder 1:19, in 1-METHYLPYRROLIDONE (NMP), stir, be configured to slurry, after on coating machine, slurry is shifted and to be coated in barrier film substrate, form the coating of 2um-10um, dry through 75 ℃ of coating machine ovens, rolling is standby.
With the barrier film assembled battery preparing, battery design capacity 20Ah, 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.
Detection method:
The low-temperature characteristics 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, battery is placed in to 0 ℃ of environment lower 2 hours, with 1C electric current by battery constant-current discharge to 2.5V, read the 1C 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, battery is placed in to-10 ℃ of environment lower 2 hours, with 1C electric current by battery constant-current discharge to 2.5V, read the 1C discharge capacity of battery.
Embodiment 2
Its preparation method is:
1, Li
3pW
12o
40-Al
2o
3the preparation of composite ceramic powder
By Al
2o
3ceramic powders and phosphotungstic acid lithium Li
3pW
12o
40the ratio of 10:5 takes in mass ratio, by Al
2o
3ceramic powders is immersed in phosphotungstic acid lithium Li
3pW
12o
40in absolute methanol solution, after 4 hours, leach, 60 ℃ of water bath methods, after preliminarily dried, then 80 ℃ 8 dried 4 hours, and then 200 ℃ of bakings are 3 hours, obtain Li
3pW
12o
40-Al
2o
3composite ceramic powder.
2, the preparation of ceramic diaphragm
According to Kynoar (PVDF, HSV900) and Li
3pW
12o
40-Al
2o
3the ratio of composite ceramic powder 1:20 stirs in 1-METHYLPYRROLIDONE (NMP), is configured to slurry, after on coating machine, slurry is shifted and to be coated in barrier film substrate, form the coating of 2um, dry through 95 ℃ of coating machine ovens, rolling is standby.
The battery assembling of the present embodiment and detection method are with embodiment 1.
Embodiment 3
1, Li
4siW
12o
40-Al
2o
3the preparation of composite ceramic powder
By Al
2o
3ceramic powders and silicotungstate lithium Li
4siW
12o
40the ratio of 10:3 takes in mass ratio, by Al
2o
3ceramic powders is immersed in silicotungstate lithium Li
4siW
12o
40in absolute methanol solution, after 24 hours, leach, 100 ℃ of water bath methods, after preliminarily dried, then 160 ℃ dried 3 hours, and then 1000 ℃ of bakings are 1 hour, obtain Li
4siW
12o
40-Al
2o
3composite ceramic powder.
2, the preparation of ceramic diaphragm
According to Kynoar (PVDF, HSV900) and Li
4siW
12o
40-Al
2o
3the ratio of composite ceramic powder 1:15, in 1-METHYLPYRROLIDONE (NMP), stir, be configured to slurry, after on coating machine, slurry is shifted and to be coated in barrier film substrate, form the coating of 10um, dry through 80 ℃ of coating machine ovens, rolling is standby.
The battery assembling of the present embodiment and detection method are with embodiment 1.
Embodiment 4
1, Li
4siMo
12o
40-Al
2o
3the preparation of composite ceramic powder
By Al
2o
3ceramic powders and silicomolybdic acid lithium Li
4siMo
12o
40the ratio of 10:1 takes in mass ratio, by Al
2o
3ceramic powders is immersed in silicomolybdic acid lithium Li
4siMo
12o
40in ethanol solution, after 12 hours, leach, 90 ℃ of water bath methods, after preliminarily dried, then 100 ℃ dried 4 hours, and then 600 ℃ of bakings are 3 hours, obtain Li
4siMo
12o
40-Al
2o
3composite ceramic powder.
2, the preparation of ceramic diaphragm
According to Kynoar (PVDF, HSV900) and Li
4siMo
12o
40-Al
2o
3the ratio of composite ceramic powder 1:10 stirs in 1-METHYLPYRROLIDONE (NMP), is configured to slurry, after on coating machine, slurry is shifted and to be coated in barrier film substrate, form the coating of 6um, dry through 80 ℃ of coating machine ovens, rolling is standby.
The battery assembling of the present embodiment and detection method are with embodiment 1.
Embodiment 5
1, Li
3pMo
12o
40-Li
3pW
12o
40-Al
2o
3the preparation of composite ceramic powder:
By phosphomolybdic acid lithium Li
3pMo
12o
40with phosphotungstic acid lithium Li
3pW
12o
40by 1:1, be mixed to form mixture, Al
2o
3ceramic powder is 10:2.5 with the ratio of mixture, by Al
2o
3ceramic powders is immersed in the ethanol solution of mixture and leaches after 12 hours, 90 ℃ of water bath methods, and after preliminarily dried, then 100 ℃ dried 4 hours, and then 600 ℃ of bakings are 3 hours, obtain Li
3pMo
12o
40-Li
3pW
12o
40-Al
2o
3composite ceramic powder.
2, the preparation of ceramic diaphragm
According to Kynoar (PVDF, HSV900) and Li
3pMo
12o
40-Li
3pW
12o
40-Al
2o
3the ratio of composite ceramic powder 1:18 stirs in 1-METHYLPYRROLIDONE (NMP), is configured to slurry, after on coating machine, slurry is shifted and to be coated in barrier film substrate, form the coating of 6um, dry through 80 ℃ of coating machine ovens, rolling is standby.
The battery assembling of the present embodiment and detection method are with embodiment 1.
Embodiment 6
Difference from Example 5 is: by phosphomolybdic acid lithium Li
3pMo
12o
40with phosphotungstic acid lithium Li
3pW
12o
40by 1:1, be mixed to form mixture, become: silicotungstate lithium Li
4siW
12o
40with silicomolybdic acid lithium Li
4siMo
12o
40by 1:1, be mixed to form mixture.
Comparative example 1
Operating procedure, with embodiment 1, is just directly used Al
2o
3powder is made carrier, without crossing polyoxometallic acid lithium salts dipping, with Al
2o
3the mass ratio of powder changes 10:3.5 into
Comparative example 2
Operating procedure, with embodiment 1, just directly adopts polyoxometallate powder Li
3pMo
12o
40after PVDF pulping, to barrier film, substrate applies, and does not add Al
2o
3powder.
Comparative example 3
Directly with polyalkene diaphragm base material, make barrier film, to barrier film, any processing is not done in substrate, is directly used for carrying out the test of physical and chemical parameter), the low-temperature characteristics of battery is tested after being made into battery.
Table 1 is the physical and chemical parameter contrast table of each embodiment and comparative example gained barrier film:
Table 2 is the low temperature discharge capacity comparison table that each embodiment and comparative example gained barrier film are made battery:
From table 1 gained physical and chemical parameter, can find out, embodiment, owing to having added polyoxometallic acid lithium salts, diminishes the aperture of barrier film, and porosity diminishes, but from the low temperature capacity comparison of table 2, containing polyoxometallic acid lithium salts-Al
2o
3the barrier film of composite coating (embodiment 1-4) is than only containing Al
2o
3the low temperature discharge capacity that the barrier film of coating (comparative example 1) is corresponding is large, has embodied the advantage of polyoxometallate; Containing polyoxometallate-Al
2o
3(embodiment 1-4) is less than the low temperature discharge capacity of the barrier film that only contains polyoxometallate coating (comparative example 2) for the barrier film of composite coating, and its reason is rigidity Al
2o
3hindered the migration of lithium ion, but without rigidity Al
2o
3barrier film cannot guarantee the fail safe of battery.
Claims (9)
1. a polyoxometallic acid lithium salts ceramic diaphragm for lithium ion battery, comprises polyalkene diaphragm base material, it is characterized in that: the surface-coated of described polyalkene diaphragm base material is containing the Al of polyoxometallic acid lithium salts
2o
3composite ceramic powder.
2. polyoxometallic acid lithium salts ceramic diaphragm for lithium ion battery according to claim 1, is characterized in that: described polyoxometallic acid lithium salts is Li
3xY
12o
40or 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. according to polyoxometallic acid lithium salts ceramic diaphragm for claim 1 lithium ion battery, it is characterized in that: described polyalkene diaphragm base material is the monofilm of polypropylene (PP), polyethylene (PE), or the trilamellar membrane being comprised of two kinds of materials.
4. the preparation method of polyoxometallic acid lithium salts ceramic diaphragm for lithium ion battery according to claim 1, is characterized in that: comprise the steps:
(1) Al
2o
3ceramic powders and the polyoxometallate in mass ratio ratio of 10:1 – 5 divide and get, and ceramic powders are immersed in the absolute methanol or ethanol solution of polyoxometallic acid lithium salts, then leach, dry, obtain polyoxometallic acid lithium salts-Al
2o
3composite ceramic powder;
(2) by Kynoar (PVDF, HSV900) and polyoxometallic acid lithium salts-Al
2o
3composite ceramic, adds in 1-METHYLPYRROLIDONE (NMP) and stirs, and is mixed into slurry;
(3) slurry step (2) being made is coated on the surface of polyalkene diaphragm base material, then dry forming.
5. the preparation method of polyoxometallic acid lithium salts ceramic diaphragm for lithium ion battery according to claim 4, is characterized in that: Al in described step (1)
2o
3ceramic powders is immersed in the absolute methanol of polyoxometallic acid lithium salts or the time of ethanol solution is 4-24 hour.
6. the preparation method of polyoxometallic acid lithium salts ceramic diaphragm for lithium ion battery according to claim 4, it is characterized in that: the drying mode in described step (1) is: first 60-100 ℃ water bath method, then 80 ℃-160 ℃ are dried 3-4 hour, last 200-1000 ℃ of baking 3 hours.
7. the preparation method of polyoxometallic acid lithium salts ceramic diaphragm for lithium ion battery according to claim 4, is characterized in that: in described step (3), slurry coating is 2um-10um to the surperficial thickness of polyalkene diaphragm base material.
8. the preparation method of polyoxometallic acid lithium salts ceramic diaphragm for lithium ion battery according to claim 4, is characterized in that: being dried in described step (3) is: the polyalkene diaphragm base material that is coated with slurry is dry through coating machine oven 75-95 ℃.
9. the preparation method of polyoxometallic acid lithium salts ceramic diaphragm for lithium ion battery according to claim 4, is characterized in that: Kynoar (PVDF, HSV900) and polyoxometallic acid lithium salts-Al in described step (2)
2o
3the ratio of composite ceramic is 1:5-20.
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| CN105957995A (en) * | 2016-06-18 | 2016-09-21 | 清华大学 | Potassium polyoxometalate ceramic membrane for lithium-ion battery |
| CN105977430A (en) * | 2016-06-18 | 2016-09-28 | 清华大学 | Polyoxometallic acid lithium salt ceramic membrane for lithium-ion battery |
| CN106099016A (en) * | 2016-06-18 | 2016-11-09 | 清华大学 | A kind of lithium ion battery multi-metal oxygen acid sodium-salt ceramic diaphragm |
| CN106410095A (en) * | 2016-06-18 | 2017-02-15 | 清华大学 | Polyoxometallic acid ammonium salt ceramic separator for lithium ion battery |
| CN105977495B (en) * | 2016-05-11 | 2018-09-04 | 中国东方电气集团有限公司 | A kind of preparation method of affluxion body in lithium ion batteries graphite paper |
| CN110600664A (en) * | 2019-10-25 | 2019-12-20 | 苏州清陶新能源科技有限公司 | Battery diaphragm, preparation method thereof and battery comprising battery diaphragm |
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