CN114256560A - Cellulose inorganic composite membrane, high-temperature-resistant battery diaphragm, and preparation method and application thereof - Google Patents
Cellulose inorganic composite membrane, high-temperature-resistant battery diaphragm, and preparation method and application thereof Download PDFInfo
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- CN114256560A CN114256560A CN202111405836.6A CN202111405836A CN114256560A CN 114256560 A CN114256560 A CN 114256560A CN 202111405836 A CN202111405836 A CN 202111405836A CN 114256560 A CN114256560 A CN 114256560A
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- cellulose
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- battery
- lithium ion
- bacterial cellulose
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 229920002678 cellulose Polymers 0.000 title claims abstract description 27
- 239000001913 cellulose Substances 0.000 title claims abstract description 27
- 239000012528 membrane Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 44
- 229920002749 Bacterial cellulose Polymers 0.000 claims abstract description 36
- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229920000620 organic polymer Polymers 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 13
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000661 sodium alginate Substances 0.000 claims description 10
- 235000010413 sodium alginate Nutrition 0.000 claims description 10
- 229940005550 sodium alginate Drugs 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 239000011147 inorganic material Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000008595 infiltration Effects 0.000 abstract description 2
- 238000001764 infiltration Methods 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 9
- 238000011049 filling Methods 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
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- 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
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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
- H01M50/491—Porosity
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a cellulose inorganic composite membrane, a high-temperature-resistant battery diaphragm, and a preparation method and application thereof, and belongs to the field of lithium ion battery manufacturing. The cellulose inorganic composite film comprises bacterial cellulose and composite powder; the composite powder comprises an organic high molecular compound and an inorganic substance; the mass ratio of the bacterial cellulose to the composite powder is 5-50: 25-200; the mass ratio of the organic polymer compound to the inorganic substance is 10-300: 100-300. The battery diaphragm of the invention has simple preparation method, no pollution in the process and low commercialization cost. The porosity and the liquid absorption rate of the battery diaphragm are high, so that the battery diaphragm is more beneficial to the infiltration and the ion migration of electrolyte; the thermal stability is excellent, so that the safety performance of the lithium ion battery is greatly improved; the lithium ion battery separator has better long cycle performance and rate cycle performance when being applied to a lithium ion battery separator, and is a separator for a lithium ion battery with great potential.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery manufacturing, and particularly relates to a cellulose inorganic composite membrane, a lithium ion battery diaphragm, and a preparation method and application thereof.
Background
With the rapid development of electric vehicles and energy storage industries, the research and development of lithium ions and batteries with high capacity, long service life, high safety and rapid charging are receiving great attention. The lithium ion battery has the characteristics of high energy density, long cycle life and no memory effect; and has the advantages of safety, environmental friendliness, reliability, rapid charge and discharge and the like, thereby becoming a hotspot of technical research in recent years.
The battery separator is an important component of the lithium ion battery, not only provides an ion transmission channel for the liquid battery, but also prevents direct contact between the cathode and the anode, and prevents the short circuit of the anode and the cathode of the battery. Currently, polyolefin separators are the primary separators due to their considerable mechanical strength, electrochemical stability and appropriate separator thickness. Currently, commercially available polyolefin separators are mainly polypropylene (PP), Polyethylene (PE), and a combination film thereof. However, separators based on polymer polyolefin such as polypropylene (PP), Polyethylene (PE), etc. have several problems, such as poor battery rate performance and thermal stability of the separator, affecting cycle life and safety performance of the battery. In the production process, the polyolefin battery diaphragm is easy to break in the winding process and shrink under high temperature, so the baking temperature before battery liquid injection cannot be too high, and once the baking temperature is too high, the diaphragm can shrink seriously to cause battery short circuit, thereby affecting the safety performance of the battery.
In recent years, the scientific community has been attempting to develop a battery separator that overcomes the lower thermal stability and poorer rate performance of commercial separators. Therefore, the technical problem to be solved in the field is to provide a high-temperature-resistant battery diaphragm.
Disclosure of Invention
The invention aims to provide a preparation method of a cellulose inorganic composite membrane.
Another object of the present invention is to provide a cellulose inorganic composite film prepared by the above preparation method.
The invention also aims to provide application of the cellulose inorganic composite membrane as a high-temperature-resistant battery diaphragm.
Another object of the present invention is to provide a lithium ion battery, wherein a battery separator of the lithium ion battery is made of the above cellulose inorganic composite film.
In order to achieve the above objects, in one aspect, the present invention provides a cellulose inorganic composite film, comprising bacterial cellulose and composite powder; the composite powder comprises an organic high molecular compound and an inorganic substance;
the mass ratio of the bacterial cellulose to the composite powder is 5-50: 25-200;
the mass ratio of the organic polymer compound to the inorganic substance is 10-300: 100-300.
Optionally, the mass ratio of the bacterial cellulose to the composite powder is 15:50, 15:100, 15:150, 25:50, 25:100, 25:150, 25:200, 35:50, 35:100, 35:150, 45:100, 45:150, 45:200, and any value therebetween.
Alternatively, the mass ratio of the organic high molecular compound to the inorganic substance is 50:100, 50:150, 50:200, 50:250, 100:150, 100:250, 150:150, 150:200, 150:250, 200:100, 200:150, 200:250, 250:100, 250:150, 250:200, 250:300, and any value between the two.
Optionally, the organic high molecular compound is selected from at least one of sodium alginate, carboxymethyl cellulose and polyacrylic acid;
the inorganic substance is at least one selected from diatomite, zeolite, kaolin and montmorillonite.
Optionally, the cellulose inorganic composite membrane has a thickness of 20-90 μm, a porosity of 13-91%, and a liquid absorption rate of 0.17-0.36 g/cm3The heat-resisting temperature is above 400 ℃.
In another aspect, the present application provides a method for preparing the above cellulose inorganic composite membrane, wherein a suspension containing bacterial cellulose and composite powder is formed into a membrane to obtain the cellulose inorganic composite membrane.
Optionally, the mass ratio of the bacterial cellulose to the composite powder in the suspension is 5-50: 25-200.
Optionally, dispersing the composite powder and the bacterial cellulose in absolute ethyl alcohol, performing ultrasonic treatment for 30-50 min to obtain a uniformly dispersed suspension solution, and performing suction filtration to form a film.
Wherein, the membrane obtained by suction filtration is a self-supporting membrane, and the prepared cellulose inorganic composite membrane is filled with inorganic particles.
Optionally, the method of preparing the composite powder comprises: mixing the raw materials containing the organic high molecular compound and the inorganic substance with water, stirring, filtering, drying and grinding to obtain the composite powder.
Optionally, the concentration of the organic high molecular compound is 0.25-1 g/L; the concentration of the inorganic substance is 0.5 to 1.5 g/L.
Optionally, before mixing the inorganic substances, drying the inorganic substances in vacuum at 100-120 ℃ for 10-12 hours;
the stirring time is 10-12 hours;
the drying is vacuum drying at 100-120 ℃ for 10-12 hours.
Optionally, the bacterial cellulose needs to be subjected to pretreatment, wherein the pretreatment comprises grinding, smashing and freeze drying of the washed bacterial cellulose.
Optionally, the washing of the bacterial cellulose comprises the following steps:
(a) stirring bacterial cellulose in a deionized water and ethanol mixed solution for 24 hours for 1 time of treatment, and repeating for 3 times;
(b) stirring the bacterial cellulose obtained by the treatment in the step (a) in an aqueous alkali at 50-60 ℃ in an oil bath for 6-8 hours, and then washing the bacterial cellulose to be neutral by using deionized water;
(c) stirring the bacterial cellulose obtained by the step (b) in a deionized water and ethanol mixed solution for 24 hours to perform 1 treatment, and repeating the treatment for 3 times;
the volume ratio of the deionized water to the ethanol is 1: 1.
Alternatively, the alkali solution is selected from one of a 0.1mol/L solution of sodium hydroxide or potassium hydroxide.
In another aspect, the application provides an application of the cellulose inorganic composite membrane prepared by the preparation method as a battery diaphragm, and the battery diaphragm has good high-temperature resistance.
The high temperature resistance means that the battery diaphragm can still keep the original safety performance under the high temperature condition.
In another aspect, the present application provides a lithium ion battery, wherein a battery diaphragm of the lithium ion battery is prepared from the cellulose inorganic composite membrane and the cellulose inorganic composite membrane obtained by the preparation method.
The beneficial effects of the invention include:
the high-temperature-resistant battery diaphragm provided by the invention is formed by compounding organic polymer fibers, organic polymers and inorganic materials, and has strong mechanical strength and good acid-base corrosion resistance. The thickness of the diaphragm is adjustable (20-90 mu m), and the normal performance of the battery is not influenced; the diaphragm can be bent at will, and is particularly suitable for wearable batteries.
The high-temperature-resistant battery diaphragm provided by the invention has the effects of isolating the positive electrode and the negative electrode, guiding lithium ions, having high ionic conductivity and good wettability to organic electrolyte, ensuring the ordered transmission of liquid, and enabling the composite diaphragm to have excellent physical properties and electrochemical properties, thereby improving the rate capability and long-term shelving performance of the battery.
The high-temperature-resistant battery diaphragm obtained by the invention has the advantages of simple preparation method, no pollution in the process, low commercialization cost and flexible operation, and is particularly suitable for low-cost large-scale energy storage lithium ion battery systems; the porosity and the liquid absorption rate of the diaphragm are high, so that the infiltration and the ion migration of electrolyte are facilitated; the thermal stability of the diaphragm is excellent, so that the safety performance of the lithium ion battery is greatly improved; after the diaphragm is applied to the lithium ion battery, the diaphragm has better long cycle performance and rate cycle performance, and is a diaphragm for the lithium ion battery with great potential.
Drawings
FIG. 1 is a scanning electron microscope image of a high temperature-resistant battery separator in example 4 of the present invention.
Figure 2 is a TGA plot of a high temperature resistant battery separator of example 4 of the present invention.
Fig. 3 is a DTG graph of the high temperature-resistant battery separator in example 4 of the present invention.
Fig. 4 is a digital photograph of the separator of the high temperature resistant battery of example 4 of the present invention after high temperature treatment at 800 ℃.
Fig. 5 is a cyclic voltammogram of the lithium iron phosphate lithium ion battery separator in example 8 of the present invention.
Fig. 6 is a long cycle performance curve for a lithium iron phosphate lithium ion battery separator in example 8 of the present invention.
Fig. 7 is a rate performance curve of the lithium iron phosphate lithium ion battery separator in example 8 of the present invention.
Fig. 8 is a plot of the cyclic voltammetry performance of the lithium iron phosphate lithium ion battery separator of comparative example 1.
Fig. 9 is a long cycle performance curve for the lithium iron phosphate lithium ion battery separator of comparative example 1.
Fig. 10 is a rate performance curve for the lithium iron phosphate lithium ion battery separator of comparative example 1.
FIG. 11 is a scanning electron microscope image of the cross section of the high temperature resistant battery separator in example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. 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
The embodiment provides a preparation method of a powder filling material for a high-temperature-resistant battery separator, wherein the preparation method comprises the following steps:
weighing 1g of sodium alginate, adding the sodium alginate into 100mL of deionized water, and stirring and dissolving the sodium alginate into a clear solution;
weighing 2g of diatomite, drying the diatomite in vacuum at 120 ℃ for 12 hours, and naturally cooling the diatomite;
adding the dried diatomite into the sodium alginate solution, stirring for 12 hours, and performing suction filtration;
and (3) drying the powder for 12 hours at 120 ℃ in vacuum, and grinding to obtain the filling powder material of the high-temperature-resistant battery diaphragm.
Example 2
The embodiment provides a preparation method of a filling powder material of a high-temperature-resistant battery separator, wherein the preparation method comprises the following steps:
weighing 2g of sodium alginate, adding the sodium alginate into 100mL of deionized water, and stirring and dissolving the sodium alginate into a clear solution;
weighing 2g of diatomite, drying the diatomite in vacuum at 120 ℃ for 12 hours, and naturally cooling the diatomite;
adding the dried diatomite into the sodium alginate solution, stirring for 12 hours, and performing suction filtration;
and (3) drying the powder for 12 hours at 120 ℃ in vacuum, and grinding to obtain the filling powder material of the high-temperature-resistant battery diaphragm.
Example 3
The embodiment provides a preparation method of bacterial cellulose fiber of a high-temperature-resistant battery separator, wherein the preparation method comprises the following steps:
shearing bacterial cellulose taken out of a refrigerator, putting the bacterial cellulose into 400mL of mixed solution with the volume ratio of water to ethanol being 1:1, cleaning, stirring for 24 hours, changing the mixed solution every 8 hours, and carrying out 3 times.
And (3) putting the cleaned bacterial cellulose into a 500mL round-bottom flask containing 300mL of 1mol/L sodium hydroxide solution, purifying for 6 hours under the condition of oil bath at 60 ℃, and cleaning to be neutral by using a mixed solution of water and ethanol in a volume ratio of 1: 1.
And (3) continuously putting the neutral bacterial cellulose into 400mL of mixed solution with the volume ratio of water to ethanol being 1:1, cleaning, stirring for 24 hours, changing the mixed solution every 8 hours, and carrying out 3 times.
And crushing the bacterial cellulose by using an analytical grinder until no obvious block is seen, and freeze-drying to obtain the bacterial cellulose fiber.
Example 4
The embodiment provides a preparation method of a high-temperature-resistant battery separator, wherein the preparation method comprises the following steps:
100mg of the powder filling material of the high-temperature-resistant battery separator prepared in example 1 and 25mg of the bacterial cellulose fiber prepared in example 3 were dispersed in 50mL of absolute ethanol, and the mixture was ultrasonically dispersed for 30 minutes to obtain a uniformly dispersed suspension. And (3) taking 12mL of the suspension, carrying out suction filtration to form a film, and drying for 12 hours at 120 ℃ in vacuum to obtain the high-temperature-resistant battery diaphragm, marked as diaphragm No. 1 and having the thickness of 79 microns.
Fig. 1 is a scanning electron microscope image of the separator 1# prepared in example 4, which shows the structure of the separator, and the separator has many pores and is suitable for storing electrolyte.
Fig. 2 and 3 show TGA and DTG test data of the separator 1# prepared in example 4, which has a thermal stability as high as 800 ℃ or higher and good thermal safety.
Fig. 4 is a digital photograph of the separator 1# prepared in example 4 after high temperature treatment at 800 ℃. After the temperature is kept at 800 ℃ for 3 minutes, the original complete shape is still kept, and the product has toughness.
Example 5
150mg of the powder filling material of the high-temperature-resistant battery separator prepared in example 1 and 25mg of the bacterial cellulose fiber prepared in example 3 were dispersed in 50mL of absolute ethanol, and the mixture was ultrasonically dispersed for 30 minutes to obtain a uniformly dispersed suspension. And (3) taking 12mL of the suspension, carrying out suction filtration to form a film, and drying for 12 hours at 120 ℃ in vacuum to obtain the high-temperature-resistant battery diaphragm, marked as diaphragm No. 2, with the thickness of 94 mu m.
Example 6
100mg of the powder filling material of the high-temperature-resistant battery separator prepared in example 1 and 35mg of the bacterial cellulose fiber prepared in example 3 were dispersed in 50mL of absolute ethanol, and the mixture was ultrasonically dispersed for 30 minutes to obtain a uniformly dispersed suspension. And (3) taking 12mL of the suspension, carrying out suction filtration to form a film, and drying for 12 hours in vacuum at 120 ℃ to obtain the high-temperature-resistant battery diaphragm, marked as diaphragm # 3, with the thickness of 86 μm.
Example 7
100mg of the powder filling material of the high-temperature-resistant battery separator prepared in example 2 and 25mg of the bacterial cellulose fiber prepared in example 3 were dispersed in 50mL of absolute ethanol, and the mixture was ultrasonically dispersed for 30 minutes to obtain a uniformly dispersed suspension. And (3) taking 12mL of the suspension, carrying out suction filtration to form a film, and drying in vacuum at 120 ℃ for 12 hours to obtain the high-temperature-resistant battery diaphragm, marked as diaphragm No. 4, with the thickness of 79 microns.
Test example
Testing porosity and liquid absorption rate by differential weight method, specifically weighing initial mass W of the diaphragm0Recording, soaking in solvent (n-butanol) for 1 hr, and weighing the diaphragm mass W after full absorption of solvent1The porosity and the liquid absorption rate were calculated by the following formulas.
Calculating a porosity formula:
calculating a liquid absorption rate formula:
wherein rho is the density of n-butanol, g/cm3；
V is the volume of the diaphragm, cm3；
W0Initial mass of the diaphragm, mg;
W1mg is the mass of the diaphragm after the solvent is absorbed.
Table 1 shows the porosity and liquid absorption rate characterization test data of the high-temperature-resistant battery separator prepared in examples 4-7 of the invention and Celgard2400PP, and the comparison shows that the porosity and the liquid absorption rate of the high-temperature-resistant battery separator prepared in the invention are higher than those of Celgard2400 PP.
The Celgard2400PP was a polypropylene separator, commercially available from Celgard corporation.
Table 1.
| Serial number | Detecting items | Porosity (%) | Liquid absorption rate (g/cm)3) |
| 1 | |
25.80881058 | 0.312427383 |
| 2 | |
24.74796238 | 0.281622853 |
| 3 | Membrane 3# | 34.15117244 | 0.368571641 |
| 4 | Septum 4# | 38.50399658 | 0.330766192 |
| 5 | Celgard 2400PP | 24.74796238 | 0.281622853 |
Example 8
The application example provides a lithium iron phosphate lithium ion battery, the battery takes the high-temperature resistant battery diaphragm provided by the embodiment 4 as a diaphragm, and the assembly of the battery comprises the following specific steps:
1) according to the following steps of 8: 1: weighing 0.4g of lithium iron phosphate, 0.05g of conductive carbon black and 0.05g of polyvinylidene fluoride (PVDF) binder according to the mass ratio of 1, using nitrogen-methyl pyrrolidone (NMP) as a dispersing agent (1.05g), and stirring and mixing uniformly by magnetic force to obtain slurry;
2) coating the slurry on an aluminum foil with the thickness of 200 mu m, drying in a 60 ℃ drying oven for 2h, and drying in a 120 ℃ vacuum drying oven for 12h to obtain a lithium iron phosphate pole piece;
3) the high-temperature-resistant battery diaphragm prepared in example 4 was cut into 19mm round pieces as battery diaphragms, and a commercial 3011R electrolyte was used as an electrolyte to assemble a button lithium iron phosphate lithium ion battery, using 1 piece of the above-described electrode sheet as a battery positive electrode, and a 200 μm commercial lithium piece as a battery negative electrode.
And (3) carrying out electrochemical performance test on the obtained lithium iron phosphate lithium ion battery, wherein a Solatron analytical 1400Celltest System electrochemical workstation is adopted in the test process, a cyclic voltammetry curve is tested, the voltage test interval is 2.5-3.8V, and the scanning rate is 0.1 mV/s.
And testing the charge-discharge long cycle performance of the obtained lithium iron phosphate lithium ion battery, wherein a LAND battery testing system is adopted in the testing process, the charge-discharge long cycle curve of the battery is tested, the voltage testing interval is 2.5-3.8V, and the charge-discharge current density is 5C.
And testing the battery charge-discharge multiplying power performance of the obtained lithium iron phosphate lithium ion battery, wherein a LAND battery testing system is adopted in the testing process, the charge-discharge multiplying power circulation curve of the battery is tested, the voltage testing interval is 2.5-3.8V, and the charge-discharge current density is 0.1, 0.5, 1, 2 and 5C.
Fig. 5 is a plot of the cyclic voltammetry performance of the lithium iron phosphate lithium ion battery separator of example 8. The CV curve with substantially symmetrical redox peaks indicates that the material performs well with less polarization.
Fig. 6 is a long cycle performance test of the lithium iron phosphate lithium ion battery separator in example 8, where the specific capacity of the lithium ion battery reaches 123.9mAh/g at a current density of 5C, and the lithium ion battery has a capacity retention rate of 98.45% after 100 cycles, which shows that the long cycle performance of the separator is good.
Fig. 7 is a rate cycle test of the lithium iron phosphate lithium ion battery separator in example 8, wherein the lithium ion battery has a specific capacity of 148.1mAh/g at a current density of 0.1C, and after multiple times of rate charging and discharging, the current returns to the initial value, the specific capacity of the battery still remains 139.7mAh/g, and the capacity retention rate is 94.33%. The battery assembled by the diaphragm prepared by the method has excellent rate charge and discharge performance.
Comparative example 1
This application example provides a lithium iron phosphate lithium ion battery assembled with a Celgard2400PP separator as the separator using the same manufacturing steps and parameters as in example 8.
Fig. 8 is a plot of the cyclic voltammetry performance of a lithium iron phosphate lithium ion battery of comparative example 1.
Figure 9 long cycle performance testing of lithium iron phosphate lithium ion batteries of comparative example 1. In a lithium iron phosphate battery, the specific capacity of the lithium ion battery reaches 123.2mAh/g under the current density of 5C, the battery capacity is obviously reduced after 100 circles, the capacity retention rate is only 94.07%, and the cycle life is short.
Fig. 10 is a rate cycle test for a lithium iron phosphate lithium ion battery of comparative example 1. In a lithium iron phosphate battery, under the current density of 0.1C, the specific capacity of the lithium ion battery reaches 146.4mAh/g, after multiple times of multiplying power charging and discharging, the current is recovered to the initial size, the specific capacity of the battery is obviously reduced, the specific capacity of the battery is 136.3mAh/g, the capacity retention rate is only 93.1%, and the multiplying power performance is poor.
The invention is not the best known technology. The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. The cellulose inorganic composite membrane is characterized in that the components of the cellulose inorganic composite membrane comprise bacterial cellulose and composite powder; the composite powder comprises an organic high molecular compound and an inorganic substance;
the mass ratio of the bacterial cellulose to the composite powder is 5-50: 25-200;
the mass ratio of the organic high molecular compound to the inorganic substance is 10-300: 100-300;
the organic high molecular compound is selected from at least one of sodium alginate, carboxymethyl cellulose and polyacrylic acid;
the inorganic matter is at least one of diatomite, zeolite, kaolin and montmorillonite.
2. The cellulose inorganic composite film according to claim 1, wherein the cellulose inorganic composite film has a thickness of 20 to 90 μm, a porosity of 13 to 91%, and a liquid absorption rate of 0.17 to 0.36g/cm3The heat-resisting temperature is more than 400 ℃.
3. A method for producing the cellulose inorganic composite film according to any one of claims 1 to 2, wherein a suspension containing bacterial cellulose and composite powder is formed into a film to obtain the cellulose inorganic composite film.
4. The preparation method according to claim 3, wherein the mass ratio of the bacterial cellulose to the composite powder in the suspension is 5-50: 25-200;
preferably, the method for preparing the composite powder comprises: mixing raw materials containing organic high molecular compounds and inorganic substances with water, stirring, filtering, drying and grinding to obtain the composite powder;
preferably, the concentration of the organic polymer compound is 0.25-1 g/L, and the concentration of the inorganic substance is 0.5-1.5 g/L.
5. The method according to claim 4, wherein the inorganic materials are dried under vacuum at 100 to 120 ℃ for 10 to 12 hours before being mixed;
the stirring time is 10-12 hours;
the drying is vacuum drying at 100-120 ℃ for 10-12 hours.
6. The preparation method according to claim 3, wherein the bacterial cellulose is subjected to a pretreatment, and the pretreatment comprises grinding, crushing and freeze-drying of the washed bacterial cellulose.
7. The method of claim 6, wherein the cleaning comprises the steps of:
(a) stirring bacterial cellulose in a deionized water and ethanol mixed solution for 24 hours for 1 time of treatment, and repeating for 3 times;
(b) stirring the bacterial cellulose obtained by the treatment in the step (a) in an aqueous alkali at 50-60 ℃ in an oil bath for 6-8 hours, and then washing the bacterial cellulose to be neutral by using deionized water;
(c) stirring the bacterial cellulose obtained by the step (b) in a deionized water and ethanol mixed solution for 24 hours to perform 1 treatment, and repeating the treatment for 3 times;
the volume ratio of the deionized water to the ethanol is 1: 1;
preferably, the alkali solution is selected from one of 0.1mol/L sodium hydroxide or potassium hydroxide solution.
8. The application of the cellulose inorganic composite membrane according to any one of claims 1 to 2 and the cellulose inorganic composite membrane prepared by the preparation method according to any one of claims 3 to 7 as a battery diaphragm.
9. A lithium ion battery is characterized in that a battery diaphragm of the lithium ion battery is prepared from the cellulose inorganic composite membrane according to any one of claims 1 to 2 and the cellulose inorganic composite membrane obtained by the preparation method according to any one of claims 3 to 7.
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| WO2023225843A1 (en) * | 2022-05-24 | 2023-11-30 | 宁德新能源科技有限公司 | Separator and preparation method therefor, electrochemical device and electronic device |
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