CN113644377A - Semisolid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry and preparation method and application thereof - Google Patents
Semisolid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry and preparation method and application thereof Download PDFInfo
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- CN113644377A CN113644377A CN202110772808.1A CN202110772808A CN113644377A CN 113644377 A CN113644377 A CN 113644377A CN 202110772808 A CN202110772808 A CN 202110772808A CN 113644377 A CN113644377 A CN 113644377A
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- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 title claims abstract description 105
- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 42
- 239000002002 slurry Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000007613 slurry method Methods 0.000 title description 2
- 239000007787 solid Substances 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000002033 PVDF binder Substances 0.000 claims abstract description 24
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 22
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011812 mixed powder Substances 0.000 claims abstract description 19
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims abstract description 15
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 14
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 13
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 238000007774 anilox coating Methods 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 24
- 230000009471 action Effects 0.000 abstract description 5
- 239000013589 supplement Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 20
- 229940113088 dimethylacetamide Drugs 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 8
- DYKZEUFKJOSFSH-UHFFFAOYSA-K P([O-])([O-])([O-])=O.[Al+3].[Li+] Chemical compound P([O-])([O-])([O-])=O.[Al+3].[Li+] DYKZEUFKJOSFSH-UHFFFAOYSA-K 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UWHSBQHWBVJPLR-UHFFFAOYSA-E P(=O)([O-])([O-])[O-].[Li+].[Li+].[Al+3].[Ti+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Li+].[Li+].[Al+3].[Ti+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] UWHSBQHWBVJPLR-UHFFFAOYSA-E 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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 preparation method of semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry, which comprises the following steps: step 1: drying ammonium dihydrogen phosphate, lithium carbonate, aluminum oxide and titanium dioxide; step 2: taking out, cooling, and then putting into a ball mill for grinding to obtain mixed powder; and step 3: carrying out step heating reaction to generate titanium lithium aluminum phosphate; and 4, step 4: taking out and cooling, and then crushing and grinding the lithium titanium aluminum phosphate to obtain lithium titanium aluminum phosphate powder; and 5: and putting the lithium titanium aluminum phosphate powder into a dimethylacetamide solution, adding polyvinylidene fluoride, adding dimethyl carbonate, and adding a tripropylene glycol solution to obtain the semi-solid lithium titanium aluminum phosphate gel electrolyte diaphragm slurry. Lithium ions are released by the titanium lithium aluminum phosphate particles in the slurry under the action of the electrolyte so as to supplement the lithium ions consumed in the electrolyte, prolong the service life of the battery and slow down the reduction of the performance of the battery.
Description
Technical Field
The invention relates to the technical field of lithium battery diaphragms, in particular to semi-solid lithium titanium phosphate lithium aluminum gel electrolyte diaphragm slurry and a preparation method and application thereof.
Background
Lithium ion batteries have different moving directions of lithium ions during charging and discharging, and the lithium ions release electrons to form a current during moving. However, lithium ions react with the electrolyte during movement, so that the lithium ions are somewhat lost. With the increase of the charging and discharging times, the quantity of lithium ions is reduced, and the performance of the battery is reduced.
Disclosure of Invention
The invention aims to provide semi-solid lithium titanium phosphate lithium aluminum gel electrolyte diaphragm slurry aiming at the technical defect that the performance of a battery is reduced due to the loss of lithium ions in the charging and discharging processes in the prior art. Lithium ions are released by the titanium lithium aluminum phosphate particles in the slurry under the action of the electrolyte so as to supplement the lithium ions consumed in the electrolyte, prolong the service life of the battery and slow down the reduction of the performance of the battery.
In another aspect of the present invention, a method for preparing the semi-solid lithium titanium aluminum phosphate gel electrolyte separator slurry is provided.
In another aspect of the present invention, a semi-solid lithium titanium aluminum phosphate gel electrolyte membrane is provided.
In another aspect of the present invention, a lithium battery is provided.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a preparation method of semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry comprises the following steps:
step 1: drying ammonium dihydrogen phosphate, lithium carbonate, aluminum oxide and titanium dioxide; the mass ratio of ammonium dihydrogen phosphate, lithium carbonate, alumina and titanium dioxide is (60-65): (8-10): (2-4): (24-26).
Step 2: taking out, cooling, and then putting into a ball mill for grinding to obtain mixed powder, wherein the particle size of the mixed powder is 0.8-1.5 μm.
And step 3: carrying out step heating reaction on the mixed powder obtained in the step 2 to generate titanium lithium aluminum phosphate; the step heating process comprises the following steps: the temperature is increased to 300 ℃ for 250-.
The chemical reaction equation involved in this step is:
and 4, step 4: taking out the lithium titanium aluminum phosphate generated by the reaction in the step 3, cooling, crushing and grinding the lithium titanium aluminum phosphate to obtain lithium titanium aluminum phosphate powder; the particle size of the lithium aluminum titanium phosphate powder is 0.1-0.9 μm.
And 5: putting the lithium aluminum titanium phosphate powder obtained in the step 4 into a dimethylacetamide solution to be dispersed to obtain a solution A; adding polyvinylidene fluoride into the solution A to obtain a solution B; adding dimethyl carbonate into the solution B to obtain a solution C; adding tripropylene glycol solution into the solution C to obtain semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry; the mass portion ratio of the titanium lithium aluminum phosphate powder, the dimethyl acetamide, the polyvinylidene fluoride, the dimethyl carbonate and the tripropylene glycol is (20-30): (49-61): (4-6): (5-10): (5-10).
In another aspect of the present invention, the semi-solid lithium titanium aluminum phosphate gel electrolyte membrane slurry prepared by the above preparation method.
In another aspect of the present invention, a semi-solid lithium titanium phosphate aluminum gel electrolyte membrane includes a base membrane and a coating layer formed of the semi-solid lithium titanium phosphate aluminum gel electrolyte membrane slurry as described above coated on one or both sides of the base membrane.
In the technical scheme, the base film is a polyethylene base film, the thickness of the base film is 12 micrometers, and the thickness of the coating is 4 micrometers; the coating mode is anilox roller coating.
In another aspect of the present invention, a lithium battery includes a positive electrode, a negative electrode, an electrolyte and the above semi-solid lithium titanium aluminum phosphate gel electrolyte membrane.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry provided by the invention, the lithium titanium phosphate aluminum powder contained in the semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry is combined with polyvinylidene fluoride, so that lithium ions can be released, and the lithium ions consumed in electrolyte can be supplemented.
2. According to the semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm provided by the invention, polyvinylidene fluoride is changed into fluffy gel under the action of the electrolyte, so that the release of lithium ions in the lithium titanium phosphate aluminum powder is facilitated.
3. The lithium battery provided by the invention can timely supplement lithium ions consumed by the electrolyte in the charging and discharging processes, and the service life of the lithium battery is prolonged.
Drawings
FIG. 1 is a scanning electron microscope image of a semi-solid lithium titanium aluminum phosphate gel electrolyte membrane prepared in example 1;
fig. 2 is a scanning electron microscope image of the lithium titanium aluminum phosphate separator prepared in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry comprises the following steps:
step 1: putting ammonium dihydrogen phosphate, lithium carbonate, aluminum oxide and titanium dioxide into a drying oven at the temperature of 150 ℃ for drying; wherein the mass ratio of ammonium dihydrogen phosphate to lithium carbonate to alumina to titanium dioxide is 60:8:2: 24;
step 2: taking out, cooling, and then putting into a ball mill for grinding to obtain mixed powder, wherein the average grain diameter of the mixed powder is 0.8 mu m, the grinding time is 4h, and the rotating speed is 500 r/min;
and step 3: putting the mixed powder obtained in the step (2) into a ceramic crucible, and then putting the ceramic crucible into a muffle furnace for step heating reaction to generate titanium lithium aluminum phosphate; the step heating process comprises the following steps: heating to 250 ℃, keeping the temperature for 2h, then continuing to heat to 450 ℃, keeping the temperature for 2h, heating to 650 ℃, keeping the temperature for 2h, and finally heating to 850 ℃ and keeping the temperature for 2 h;
and 4, step 4: taking out the lithium titanium aluminum phosphate solid generated by the reaction in the step 3, cooling, crushing the lithium titanium aluminum phosphate, adding the crushed lithium titanium aluminum phosphate into a ball mill, and grinding to obtain lithium titanium aluminum phosphate powder, wherein the average particle size of the obtained lithium titanium aluminum phosphate powder is 0.1 mu m, the grinding time is 4h, and the rotating speed is 1000 r/min;
and 5: putting the lithium aluminum titanium phosphate powder obtained in the step 4 into a dimethylacetamide solution, stirring for 25min, and then sanding for 15min by using a pin type sanding machine, wherein the sanding speed is 500r/min to obtain a solution A; adding polyvinylidene fluoride into the solution A, and stirring for 30min to dissolve the polyvinylidene fluoride to obtain a solution B; adding dimethyl carbonate into the solution B, and stirring for 20min to obtain a solution C; adding a tripropylene glycol solution into the solution C, and stirring for 20min to prepare semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry; the lithium aluminum phosphate powder comprises, by mass, 20 parts of lithium aluminum phosphate powder, 61 parts of dimethylacetamide, 4 parts of polyvinylidene fluoride, 5 parts of dimethyl carbonate and 10 parts of tripropylene glycol.
And coating the semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry on a polyethylene base film through a reticulate pattern roller, and then extracting and drying to obtain the semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm.
The specification of the polyethylene base film is 1000mm multiplied by 12 mu m; the specification of the anilox roller is 1150mm multiplied by 100mm multiplied by 4 mu m; the coating thickness was 4 μm.
The extraction is carried out by the following steps: dividing the extraction tank into 10 small tanks, wherein the depth of each tank is 1m, extracting liquid in which deionized water and dimethylacetamide are mixed according to different mass ratios is arranged in the first three tanks to form a coagulating bath, the mass ratio of dimethylacetamide to water in the first tank is 3:2, the mass ratio of dimethylacetamide to water in the second tank is 1:1, the mass ratio of dimethylacetamide to water in the third tank is 2:3, and deionized water is arranged in the rest other tanks, so that a diaphragm penetrates through each tank, and the three coagulating baths and the deionized water with different concentrations are sequentially used for extraction.
Fig. 1 is a scanning electron microscope image of the surface of the semi-solid lithium titanium phosphate aluminum gel electrolyte membrane in this example. As can be seen from the figure, the polyvinylidene fluoride net is more uniform, and the lithium aluminum titanium phosphate particles are absorbed into the polyvinylidene fluoride net structure in a finer way; when the lithium ion battery is immersed in electrolyte, the net structure is changed into gel, so that the titanium lithium aluminum phosphate is looser, lithium ions are released more easily, and the lost lithium ions are replenished.
Comparative example 1
This comparative example is based on the slurry system in example 1 with PVDF replaced with a 10% meta-aramid solution.
A preparation method of titanium lithium aluminum phosphate diaphragm slurry comprises the following steps:
step 1: putting ammonium dihydrogen phosphate, lithium carbonate, aluminum oxide and titanium dioxide into a drying oven at the temperature of 150 ℃ for drying; wherein the mass ratio of ammonium dihydrogen phosphate to lithium carbonate to alumina to titanium dioxide is 60:8:2: 24;
step 2: taking out, cooling, and then putting into a ball mill for grinding to obtain mixed powder, wherein the average grain diameter of the mixed powder is 0.8 mu m, the grinding time is 4h, and the rotating speed is 500 r/min;
and step 3: putting the mixed powder obtained in the step (2) into a ceramic crucible, and then putting the ceramic crucible into a muffle furnace for step heating reaction to generate titanium lithium aluminum phosphate; the step heating process comprises the following steps: heating to 250 ℃, keeping the temperature for 2h, then continuing to heat to 450 ℃, keeping the temperature for 2h, heating to 650 ℃, keeping the temperature for 2h, and finally heating to 850 ℃ and keeping the temperature for 2 h;
and 4, step 4: taking out the lithium titanium aluminum phosphate solid generated by the reaction in the step 3, cooling, crushing the lithium titanium aluminum phosphate, adding the crushed lithium titanium aluminum phosphate into a ball mill, and grinding to obtain lithium titanium aluminum phosphate powder, wherein the average particle size of the obtained lithium titanium aluminum phosphate powder is 0.1 mu m, the grinding time is 4h, and the rotating speed is 1000 r/min;
and 5: putting the lithium aluminum titanium phosphate powder obtained in the step 4 into a dimethylacetamide solution, stirring for 25min, and then sanding for 15min by using a pin type sanding machine, wherein the sanding speed is 500r/min to obtain a solution A; adding 10% meta-aramid dissolving solution into the solution A, and stirring for 30min to obtain solution B; adding dimethyl carbonate into the solution B, and stirring for 20min to obtain a solution C; adding a tripropylene glycol solution into the solution C, and stirring for 20min to prepare titanium lithium aluminum phosphate gel electrolyte diaphragm slurry; the lithium aluminum phosphate powder comprises, by mass, 20 parts of lithium aluminum phosphate powder, 61 parts of dimethylacetamide, 4 parts of a 10% meta-aramid dissolving solution, 5 parts of dimethyl carbonate and 10 parts of tripropylene glycol.
The lithium titanium aluminum phosphate diaphragm slurry is coated on a polyethylene base film through an anilox roller by the same method as in example 1, and then extracted and dried to obtain the lithium titanium aluminum phosphate diaphragm.
Fig. 2 is a scanning electron microscope image of the lithium titanium aluminum phosphate separator prepared in the present comparative example. As can be seen from fig. 2, the m-aramid fiber bonds the titanium lithium aluminum phosphate powder together to form a coarse block. The structure hardly changes under the action of electrolyte, and lithium ions are not easily released.
Comparative example 2
This comparative example is based on the slurry system of example 1, replacing lithium aluminum titanium phosphate powder with alumina powder.
A preparation method of alumina diaphragm slurry comprises the steps of putting alumina powder into a dimethylacetamide solution, stirring for 25min, and sanding for 15min by using a pin type sanding machine at a sanding speed of 500r/min to obtain a solution A; adding polyvinylidene fluoride into the solution A, and stirring for 30min to dissolve the polyvinylidene fluoride to obtain a solution B; adding dimethyl carbonate into the solution B, and stirring for 20min to obtain a solution C; adding a tripropylene glycol solution into the solution C, and stirring for 20min to prepare alumina diaphragm slurry; the aluminum oxide powder comprises, by mass, 20 parts of aluminum oxide powder, 61 parts of dimethylacetamide, 4 parts of polyvinylidene fluoride, 5 parts of dimethyl carbonate and 10 parts of tripropylene glycol.
And coating the alumina powder diaphragm slurry on a polyethylene base film through an anilox roller, and then extracting and drying to obtain the alumina diaphragm.
Example 2
A preparation method of semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry comprises the following steps:
step 1: putting ammonium dihydrogen phosphate, lithium carbonate, aluminum oxide and titanium dioxide into an oven with the temperature of 180 ℃ for drying; wherein the mass ratio of ammonium dihydrogen phosphate to lithium carbonate to alumina to titanium dioxide is 63:9:3: 25;
step 2: taking out, cooling, and then putting into a ball mill for grinding to obtain mixed powder, wherein the average particle size of the obtained mixed powder is 1 mu m, the grinding time is 5h, and the rotating speed is 500 r/min;
and step 3: putting the mixed powder obtained in the step (2) into a ceramic crucible, and then putting the ceramic crucible into a muffle furnace for step heating reaction to generate titanium lithium aluminum phosphate; the step heating process comprises the following steps: heating to 300 ℃, keeping the temperature for 2h, then continuing to heat to 500 ℃, keeping the temperature for 2h, heating to 700 ℃ again, keeping the temperature for 2h, and finally heating to 900 ℃ and keeping the temperature for 2 h;
and 4, step 4: taking out the lithium titanium aluminum phosphate solid generated by the reaction in the step 3, cooling, crushing the lithium titanium aluminum phosphate, adding the crushed lithium titanium aluminum phosphate into a ball mill, and grinding to obtain lithium titanium aluminum phosphate powder, wherein the average particle size of the obtained lithium titanium aluminum phosphate powder is 0.5 mu m, the grinding time is 5h, and the rotating speed is 900 r/min;
and 5: putting the lithium aluminum titanium phosphate powder obtained in the step 4 into a dimethylacetamide solution, stirring for 35min, and then sanding for 25min by using a pin type sanding machine, wherein the sanding speed is 500r/min to obtain a solution A; adding polyvinylidene fluoride into the solution A, and stirring for 40min to dissolve the polyvinylidene fluoride to obtain a solution B; adding dimethyl carbonate into the solution B, and stirring for 25min to obtain a solution C; adding a tripropylene glycol solution into the solution C, and stirring for 25min to prepare semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry; the lithium aluminum titanium phosphate powder comprises, by mass, 25 parts of dimethylacetamide, 5 parts of polyvinylidene fluoride, 8 parts of dimethyl carbonate and 8 parts of tripropylene glycol.
The semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry is prepared according to the method in the embodiment 1 to obtain the semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm.
Example 3
A preparation method of semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry comprises the following steps:
step 1: putting ammonium dihydrogen phosphate, lithium carbonate, aluminum oxide and titanium dioxide into a drying oven at the temperature of 200 ℃ for drying; wherein the mass ratio of ammonium dihydrogen phosphate to lithium carbonate to alumina to titanium dioxide is 65:10:4: 26;
step 2: taking out, cooling, and then putting into a ball mill for grinding to obtain mixed powder, wherein the average particle size of the obtained mixed powder is 1.5 mu m, the grinding time is 6h, and the rotating speed is 500 r/min;
and step 3: putting the mixed powder obtained in the step (2) into a ceramic crucible, and then putting the ceramic crucible into a muffle furnace for step heating reaction to generate titanium lithium aluminum phosphate; the step heating process comprises the following steps: heating to 350 ℃, keeping the temperature for 2h, then continuing to heat to 550 ℃, keeping the temperature for 2h, heating to 750 ℃ again, keeping the temperature for 2h, and finally heating to 950 ℃ and keeping the temperature for 2 h;
and 4, step 4: taking out the lithium titanium aluminum phosphate solid generated by the reaction in the step 3, cooling, crushing the lithium titanium aluminum phosphate, adding the crushed lithium titanium aluminum phosphate into a ball mill, and grinding to obtain lithium titanium aluminum phosphate powder, wherein the average particle size of the obtained lithium titanium aluminum phosphate powder is 0.9 mu m, the grinding time is 6h, and the rotating speed is 800 r/min;
and 5: putting the lithium aluminum titanium phosphate powder obtained in the step 4 into a dimethylacetamide solution, stirring for 45min, and then sanding for 30min by using a pin type sanding machine, wherein the sanding speed is 500r/min to obtain a solution A; adding polyvinylidene fluoride into the solution A, and stirring for 50min to dissolve the polyvinylidene fluoride to obtain a solution B; adding dimethyl carbonate into the solution B, and stirring for 30min to obtain a solution C; adding a tripropylene glycol solution into the solution C, and stirring for 30min to prepare semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry; the lithium aluminum phosphate powder comprises, by mass, 30 parts of lithium aluminum phosphate powder, 49 parts of dimethylacetamide, 6 parts of polyvinylidene fluoride, 10 parts of dimethyl carbonate and 5 parts of tripropylene glycol.
The semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry is prepared according to the method in the embodiment 1 to obtain the semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm.
The semi-solid lithium titanium phosphate aluminum gel electrolyte separator prepared in examples 1-3 had the following performance parameters:
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Thickness (μm) | 16.3 | 16.5 | 16.2 | 16.5 | 16.3 |
| Breathable (Sec/100ml) | 152 | 160 | 158 | 172 | 165 |
| Tensile Strength (kgf/cm)2) | 1864 | 1866 | 1911 | 1552 | 1536 |
| 130 x h shrinkage (%) | 3.1 | 3.0 | 3.2 | 3.1 | 3.0 |
| Adhesion to Pole pieces (N) | 103 | 98 | 101 | 2.1 | 3.3 |
| Diaphragm ionic conductivity (mS/cm) | 2.9 | 2.8 | 3.1 | 1.8 | 1.4 |
Comparative example 1 differs from example 1 in that PVDF was replaced with a 10% meta-aramid solution, and as can be seen from the table above, the membrane base properties (air permeability, tensile strength and shrinkage) did not change much, but differed greatly from the pole piece adhesion and membrane ionic conductivity. This is because the polyvinylidene fluoride of the separator prepared in example 1 is changed into a fluffy gel under the action of the electrolyte, which is favorable for releasing lithium ions in the lithium aluminum titanium phosphate powder.
Compared with the example 1, the aluminum oxide powder replaces the lithium aluminum titanium phosphate powder, so that the basic performance (air permeability, tensile strength and shrinkage rate) of the diaphragm is not greatly changed, but the basic performance is greatly different from the adhesion of a pole piece and the ionic conductivity of the diaphragm. This is because the gel lithium titanium aluminum phosphate has a large amount of lithium ions released in the separator, and because the lithium ions are released from the lithium titanium aluminum phosphate solid, the lithium ion pores are left on the lithium titanium aluminum phosphate solid in the gel state, so that the lithium ions are more unblocked in the shuttling process.
Method for testing ionic conductivity of separator: two metal sheets were stacked together with an example diaphragm in between. Then putting the prepared sample into electrolyte, connecting two metal sheets to an electrochemical analyzer, then carrying out conductivity test, wherein the test results are divided into three types, namely a layer of diaphragm between metal layers, two layers of diaphragms and three layers of diaphragms, and averaging according to the number of layers (the manufacturer of the electrochemical analyzer is Shanghai Chenghua apparatus Co., Ltd., model number CHI 660E).
Example 4
The semi-solid lithium titanium phosphate aluminum gel electrolyte membranes prepared in examples 1-3 were fabricated into lithium batteries and tested for performance. Wherein the anode is lithium iron phosphate, the cathode is graphite, and the electrolyte is lithium hexafluorophosphate.
The test results are shown in the following table:
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Number of cycles | 1000 | 1000 | 1000 | 1000 | 1000 |
| Decay in discharge capacity (%) | 98％ | 99％ | 98％ | 86％ | 71％ |
The above data clearly show that the change attenuation of the discharge capacity of the battery after the battery is cycled for 1000 times in the example is very small, and the gel-state semi-solid electrolyte is proved to be very effective in improving the capacity retention rate of the battery.
The semi-solid lithium titanium phosphate aluminum gel electrolyte separator slurry of the present invention was prepared with process parameter adjustments according to the present disclosure and exhibited substantially the same performance as example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of semisolid lithium titanium aluminum phosphate gel electrolyte diaphragm slurry is characterized by comprising the following steps: the method comprises the following steps:
step 1: drying ammonium dihydrogen phosphate, lithium carbonate, aluminum oxide and titanium dioxide;
step 2: cooling, and then grinding to obtain mixed powder;
and step 3: carrying out step heating reaction on the mixed powder obtained in the step 2 to generate titanium lithium aluminum phosphate;
and 4, step 4: cooling the lithium titanium aluminum phosphate generated by the reaction in the step 3, and then crushing and grinding the lithium titanium aluminum phosphate to obtain lithium titanium aluminum phosphate powder;
and 5: putting the lithium aluminum titanium phosphate powder obtained in the step 4 into a dimethylacetamide solution to be dispersed to obtain a solution A; adding polyvinylidene fluoride into the solution A to obtain a solution B; adding dimethyl carbonate into the solution B to obtain a solution C; and adding a tripropylene glycol solution into the solution C to obtain semi-solid lithium titanium phosphate aluminum gel electrolyte diaphragm slurry.
2. The method of claim 1, wherein: in the step 1, the mass ratio of ammonium dihydrogen phosphate, lithium carbonate, alumina and titanium dioxide is (60-65): (8-10): (2-4): (24-26).
3. The method of claim 1, wherein: in the step 2, the particle size of the mixed powder is 0.8-1.5 μm.
4. The method of claim 1, wherein: in step 3, the step heating process comprises: the temperature is increased to 300 ℃ for 250-.
5. The method of claim 1, wherein: in step 4, the particle size of the lithium aluminum titanium phosphate powder is 0.1-0.9 μm.
6. The method of claim 1, wherein: in the step 5, the mass part ratio of the titanium lithium aluminum phosphate powder, the dimethylacetamide, the polyvinylidene fluoride, the dimethyl carbonate and the tripropylene glycol is (20-30): (49-61): (4-6): (5-10): (5-10).
7. The semi-solid lithium titanium aluminum phosphate gel electrolyte separator slurry prepared by the preparation method according to any one of claims 1 to 6.
8. A semi-solid lithium titanium phosphate aluminum gel electrolyte separator comprising a base film and a coating layer formed of the semi-solid lithium titanium phosphate aluminum gel electrolyte separator slurry of claim 7 coated on one or both sides of the base film.
9. The semi-solid lithium titanium phosphate aluminum gel electrolyte membrane of claim 8, wherein said base membrane is a polyethylene base membrane;
the coating mode is anilox roller coating.
10. A lithium battery comprising a positive electrode, a negative electrode, an electrolyte and the semi-solid lithium titanium phosphate aluminum gel electrolyte membrane of claim 9.
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