CN115548575B - Baking-free all-inorganic lithium ion battery diaphragm and preparation method thereof - Google Patents
Baking-free all-inorganic lithium ion battery diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN115548575B CN115548575B CN202211157396.1A CN202211157396A CN115548575B CN 115548575 B CN115548575 B CN 115548575B CN 202211157396 A CN202211157396 A CN 202211157396A CN 115548575 B CN115548575 B CN 115548575B
- Authority
- CN
- China
- Prior art keywords
- inorganic
- diaphragm
- ion battery
- lithium ion
- baking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 17
- 239000011707 mineral Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000000835 fiber Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 26
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 25
- 235000019353 potassium silicate Nutrition 0.000 claims description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical group [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000000748 compression moulding Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- 235000010755 mineral Nutrition 0.000 claims description 11
- 229920002748 Basalt fiber Polymers 0.000 claims description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- 235000012255 calcium oxide Nutrition 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- 239000010451 perlite Substances 0.000 claims description 7
- 235000019362 perlite Nutrition 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052621 halloysite Inorganic materials 0.000 claims description 5
- 229910052625 palygorskite Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 238000010025 steaming Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007767 bonding agent Substances 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005524 ceramic coating Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000008093 supporting effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 Polyethylene Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011226 reinforced ceramic Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- H01M50/403—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
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a baking-free all-inorganic lithium ion battery diaphragm and a preparation method thereof, belonging to the field of diaphragm materials. The method selects the mineral with a porous structure as a main material, and bonds and forms the mineral material by means of the bonding effect of the inorganic siliceous bonding agent. Then, the reaction activity of the functional auxiliary agent is utilized to carry out oxygen steaming under the low-temperature and low-pressure condition, and the functional auxiliary agent is excited to carry out chemical reaction with the mineral material to generate silicate substances, so that the mechanical property of the all-inorganic diaphragm is enhanced. At the same time, the mechanical property of the diaphragm is further enhanced by using the toughening fiber. The method avoids the high-temperature sintering process commonly used for preparing the inorganic diaphragm, greatly reduces the production energy consumption, simplifies the preparation process, is beneficial to reducing the production cost of the all-inorganic diaphragm and promotes the popularization of products. The baking-free process of the all-inorganic diaphragm can avoid the damage of high temperature to the porous mineral structure, retain the porous structure of the porous mineral and improve the high-current charge-discharge capacity and the cycling stability of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery diaphragms, and particularly relates to a lithium ion battery diaphragm which is easy to produce, high-temperature resistant, suitable for high-current charge and discharge and long in cycle and a preparation method thereof.
Background
With the progress of science and technology and the development of society and the increasing attention of people to environmental protection, electric energy is used as a high-efficiency and easily-obtained clean energy source, the application range of the electric energy is wider and wider, and especially the market of new energy automobiles is gradually expanding due to the continuous rising of oil prices and the increasing of the degree of environmental pollution control of the country in recent years. Therefore, the field of new energy automobiles puts higher requirements on lithium ion batteries.
As a separator material of an important composition of a lithium ion battery, it has a main role of separating the positive and negative electrodes of the battery to prevent short circuits, and also has a role of allowing electrolyte lithium ions to pass through. The performance of the separator directly affects the cycling capacity, usability and safety of the lithium ion battery. At present, most of commercial lithium ion battery separators are Polyethylene (PE) and polypropylene/polyethylene (PP/PE) separators, which mainly benefit from excellent mechanical properties and electrochemical stability, but meanwhile, due to the low melting point of the polymer, the polyolefin separator has poor high-temperature tolerance, which is mainly characterized in that the polyolefin separator has poor thermal shrinkage in an electrolyte environment and large shrinkage rate, so that high-temperature thermal failure of the battery is easily caused, internal short circuit fire of the battery is further caused, and potential safety hazards are caused. Therefore, development of lithium ion battery separators which are easy to produce, resistant to high temperature and suitable for long-cycle high-current charge and discharge has become an urgent need of the industry.
Currently, improvements in thermal stability of polyolefin separators have focused mainly on the way in which they are coated with a coating. In recent years, the use of inorganic ceramic particles for coating has become the preferred mode, and this has been due to the excellent thermal stability of the ceramic coating, which can significantly increase the thermal stability of the separator at high temperatures. Ceramic particles that are widely used at present include alumina, silica, titania, zirconia, boehmite, and the like. As reported in patent CN201610753471.9, a coated separator, which combines good air permeability and adhesive strength, was prepared using a polyolefin porous film as a matrix and alumina particles, polyacrylate and nanocellulose as ceramic coatings. On this basis, patent CN202010774162.6 reports a scheme of coating oxide ceramic particles and lithium compound particles on both sides of a base film at the same time, which effectively improves the interfacial compatibility of an electrolyte/electrode while enhancing the thermal stability of a ceramic separator. With the progress of technology, in order to eliminate the limitation of the polyolefin membrane itself on the thermal stability of the material and the unavoidable problem of shedding of the ceramic coating, ceramic membranes with fiber as a supporting structure have also begun to appear. As reported in patent CN202010537383.1, alumina fiber is used as a supporting structure, and inorganic ceramic powder is directly coated on the surface of the supporting structure to prepare a fiber reinforced ceramic diaphragm, which has good structural stability and chemical stability in high-temperature environment. Further, in order to obtain better mechanical strength and bonding strength, the patent CN202010806327.3 directly adopts inorganic nano powder as a raw material, and prepares a novel ceramic diaphragm in a hot press molding mode after adding a binder and a plasticizer, so that the novel ceramic diaphragm has extremely high porosity and heat resistance, and can greatly improve the safety use performance of a lithium ion battery. In order to further eliminate the influence of the organic binder on the thermal stability of the diaphragm, patent CN202010332682.1 and patent CN202010332684.0 report that the inorganic mineral is used as a main material, and the full inorganic ceramic diaphragm is prepared through a high-temperature sintering process, and the ceramic diaphragm has excellent thermal stability and excellent physicochemical properties, and the rate capability and the cycle capability of the lithium ion battery are obviously improved. However, the preparation of the all-inorganic ceramic membrane requires continuous firing for 4-7 hours at a high temperature of 500-800 ℃, has high energy consumption, and is unfavorable for reducing the production cost and large-scale popularization.
Disclosure of Invention
The invention provides a preparation method of a novel all-inorganic diaphragm, which is not molded by a high-temperature firing method, and realizes the preparation of the inorganic diaphragm with good bonding strength by combining the combination of an inorganic binder and a functional auxiliary agent and matching with low-temperature low-pressure oxygen steaming maintenance.
Therefore, the invention is realized by the following technical scheme:
mineral powder, toughening fiber, inorganic binder and functional auxiliary agent according to the mass ratio of 80-100:3-15:12-20:5-10, uniformly mixing, compression molding, naturally drying, placing the formed dried blank in a standard steam curing box for curing treatment, then placing the cured sample in 0.05-2mol/L dilute sulfuric acid for soaking for 2-6 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm; the mineral powder is one or more of diatomite, halloysite, palygorskite and expanded perlite; the toughening fiber is one of glass fiber and basalt fiber; the inorganic binder is one or more of sodium silicate water glass, lithium silicate water glass and alkaline silica sol; the functional auxiliary agent is quicklime or slaked lime; the curing treatment conditions are that the preset temperature of a standard steam curing box is 120-180 ℃, the pressure is set to be 1.0-1.5MPa, and the curing time is 2-8 hours; the concentration of the sodium silicate water glass or the lithium silicate water glass is 32-47%; the concentration of the alkaline silica sol is 25-33%.
The beneficial effects are that: the invention uses the characteristic of the self porous structure of the porous mineral, selects the porous mineral as the main material of the all-inorganic diaphragm, and bonds and forms the mineral main material by the bonding effect of the inorganic siliceous bonding agent. Then, the reaction activity of the functional auxiliary agent is utilized to carry out oxygen steaming under the low-temperature and low-pressure condition, and the functional auxiliary agent is excited to carry out chemical reaction with the mineral main body material to generate silicate substances so as to enhance the mechanical property of the all-inorganic diaphragm. The method does not use a high-temperature calcination process, greatly reduces the production energy consumption, simplifies the preparation process, is beneficial to reducing the production cost of the all-inorganic diaphragm and promotes the popularization of products. Meanwhile, the baking-free process of the all-inorganic diaphragm can avoid damage to the porous mineral structure by high temperature, is favorable for retaining the porous structure of the porous mineral, and constructs the all-inorganic diaphragm with a three-dimensional pore structure, thereby promoting the transmission of lithium ions in the diaphragm, improving the electrochemical performance of an assembled battery, and improving the high-current charge and discharge effect and long-term cycle stability of the lithium ion battery.
Drawings
FIG. 1 is a scanning electron microscope photograph of a baking-free all-inorganic lithium ion battery diaphragm
Detailed Description
The invention will be described in further detail with reference to examples:
mineral powder (one or more of diatomite, halloysite, palygorskite and expanded perlite), toughening fiber (one of glass fiber and basalt fiber), inorganic binder (one or more of sodium silicate water glass, lithium silicate water glass and alkaline silica sol), and functional auxiliary agent (quicklime or slaked lime) according to the mass ratio of 80-100:3-15:12-20:5-10, uniformly mixing, compression molding, naturally drying, placing the formed dried blank body in a standard steam curing box with the temperature of 120-180 ℃ and the pressure of 1.0-1.5MPa for 2-8 hours, then placing the cured sample in 0.05-2mol/L dilute sulfuric acid for soaking for 2-6 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm.
Example 1
Diatomite, glass fibers, sodium silicate water glass with the concentration of 32 percent and quicklime according to the mass ratio of 80:15:15:7, uniformly mixing, compression molding, naturally drying, placing the formed dried blank body in a standard steam curing box with the temperature of 120 ℃ and the pressure of 1.5MPa for curing treatment for 5 hours, placing the cured sample in dilute sulfuric acid with the concentration of 1.50mol/L for soaking for 3 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm.
Example 2
Diatomite, basalt fiber, 44% lithium silicate water glass and quicklime according to the mass ratio of 80:15:17:5, uniformly mixing, compression molding, naturally drying, placing the formed dried blank body in a standard steam curing box with the temperature of 120 ℃ and the pressure of 1.5MPa for curing treatment for 5 hours, placing the cured sample in dilute sulfuric acid with the concentration of 1.50mol/L for soaking for 3 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm.
Example 3
Halloysite, basalt fiber, alkaline silica sol with the concentration of 25%, and slaked lime according to the mass ratio of 100:3:18:6, uniformly mixing, compression molding, naturally drying, placing the formed dried blank body in a standard steam curing box with the temperature of 180 ℃ and the pressure of 1.0MPa for curing treatment for 8 hours, placing the cured sample in dilute sulfuric acid with the concentration of 0.05mol/L for soaking for 6 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm.
Example 4
Halloysite, basalt fiber, 32% lithium silicate water glass and slaked lime according to the mass ratio of 100:3:14:9, uniformly mixing, compression molding, naturally drying, placing the formed dried blank body in a standard steam curing box with the temperature of 180 ℃ and the pressure of 1.0MPa for curing treatment for 8 hours, placing the cured sample in dilute sulfuric acid with the concentration of 0.05mol/L for soaking for 6 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm.
Example 5
Palygorskite, glass fiber, 47% lithium silicate water glass and slaked lime according to the mass ratio of 90:10:12:10, uniformly mixing, compression molding, naturally drying, placing the formed dried blank body in a standard steam curing box with the temperature of 160 ℃ and the pressure of 1.2MPa for 2 hours of curing treatment, placing the cured sample in 2mol/L dilute sulfuric acid for soaking for 2 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm.
Example 6
Palygorskite, basalt fiber, sodium silicate water glass with the concentration of 47%, and slaked lime according to the mass ratio of 95:5:12:10, uniformly mixing, compression molding, naturally drying, placing the formed dried blank body in a standard steam curing box with the temperature of 160 ℃ and the pressure of 1.2MPa for 2 hours of curing treatment, placing the cured sample in 2mol/L dilute sulfuric acid for soaking for 2 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm.
Example 7
Expanded perlite, glass fiber, 36% sodium silicate water glass and slaked lime according to the mass ratio of 95:5:20:5, uniformly mixing, compression molding, naturally drying, placing the formed dried blank body in a standard steam curing box with the temperature of 140 ℃ and the pressure of 1.4MPa for curing treatment for 6 hours, placing the cured sample in dilute sulfuric acid with the concentration of 1.0mol/L for soaking for 4 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm.
Example 8
Expanded perlite, basalt fiber, 36% lithium silicate water glass and slaked lime according to the mass ratio of 85:13:20:5, uniformly mixing, compression molding, naturally drying, placing the formed dried blank body in a standard steam curing box with the temperature of 140 ℃ and the pressure of 1.4MPa for curing treatment for 6 hours, placing the cured sample in dilute sulfuric acid with the concentration of 1.0mol/L for soaking for 4 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm.
Example 9
Expanded perlite, basalt fiber, alkaline silica sol with the concentration of 33 percent and quicklime according to the mass ratio of 90:10:18:6, uniformly mixing, compression molding, naturally drying, placing the formed dried blank body in a standard steam curing box with the temperature of 150 ℃ and the pressure of 1.3MPa for 7 hours of curing treatment, placing the cured sample in 0.8mol/L dilute sulfuric acid for soaking for 5 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm.
Example 10
Expanded perlite, glass fiber, 29% alkaline silica sol and quicklime according to the mass ratio of 88:12:15:9, uniformly mixing, compression molding, naturally drying, placing the formed dried blank body in a standard steam curing box with the temperature of 150 ℃ and the pressure of 1.3MPa for 7 hours of curing treatment, placing the cured sample in 0.50mol/L dilute sulfuric acid for soaking for 5 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm.
The baking-free all-inorganic lithium ion battery separators prepared in examples 1 to 10 were subjected to flexural strength and porosity tests, and the batteries were tested for rate performance and cycle performance by using the inorganic separators assembled into lithium iron phosphate batteries, and the test results are shown in table 1. The results show that the baking-free all-inorganic lithium ion battery separator prepared in each embodiment has good physical properties and electrochemical properties. Compared with other samples, the baking-free all-inorganic lithium ion battery separator prepared in the embodiment 3 has better physical performance and electrochemical performance than the separators prepared in other embodiments, and the embodiment 3 has optimal preparation conditions.
Table 1 results of physical and electrochemical property testing of the baking-free all-inorganic lithium ion battery separator
Claims (3)
1. The preparation method of the baking-free all-inorganic lithium ion battery diaphragm is characterized by comprising the following steps of:
mineral powder, toughening fiber, inorganic binder and functional auxiliary agent according to the mass ratio of 80-100:3-15:12-20:5-10, uniformly mixing, compression molding, naturally drying, placing the formed dried blank in a standard steam curing box for curing treatment, then placing the cured sample in 0.05-2mol/L dilute sulfuric acid for soaking for 2-6 hours, then cleaning the sample to be neutral, and drying to obtain the baking-free all-inorganic lithium ion battery diaphragm; the mineral powder is one or more of diatomite, halloysite, palygorskite and expanded perlite; the toughening fiber is one of glass fiber and basalt fiber; the inorganic binder is one or more of sodium silicate water glass, lithium silicate water glass and alkaline silica sol; the functional auxiliary agent is quicklime or slaked lime; the curing treatment condition is that the preset temperature of a standard steam curing box is 120-180 ℃, the pressure is set to be 1.0-1.5MPa, and the curing time is 2-8 hours.
2. The method for preparing the baking-free all-inorganic lithium ion battery diaphragm, which is disclosed in claim 1, is characterized in that: the concentration of the sodium silicate water glass or the lithium silicate water glass is 32-47%; the concentration of the alkaline silica sol is 25-33%.
3. A baking-free all-inorganic lithium ion battery diaphragm is characterized in that: a process according to any one of claims 1-2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211157396.1A CN115548575B (en) | 2022-09-22 | 2022-09-22 | Baking-free all-inorganic lithium ion battery diaphragm and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211157396.1A CN115548575B (en) | 2022-09-22 | 2022-09-22 | Baking-free all-inorganic lithium ion battery diaphragm and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115548575A CN115548575A (en) | 2022-12-30 |
| CN115548575B true CN115548575B (en) | 2024-04-12 |
Family
ID=84730614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211157396.1A Active CN115548575B (en) | 2022-09-22 | 2022-09-22 | Baking-free all-inorganic lithium ion battery diaphragm and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115548575B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014123344A1 (en) * | 2013-02-06 | 2014-08-14 | Lee Jong-Hak | Natural substance area-enlarging uncoated natural wallpaper |
| CN108046680A (en) * | 2017-12-01 | 2018-05-18 | 界首市森威保温建材有限公司 | The high-quality energy saving processing technology of expanded perlite thermal-nsulation plate |
| CN108232089A (en) * | 2018-01-05 | 2018-06-29 | 吉林大学 | A kind of lithium ion battery diatomite diaphragm and preparation method thereof |
| CN108780914A (en) * | 2016-02-25 | 2018-11-09 | 旭化成株式会社 | Nonaqueous electrolyte battery inorganic particle and nonaqueous electrolyte battery |
| JP2018200795A (en) * | 2017-05-26 | 2018-12-20 | 旭化成株式会社 | Inorganic particles for nonaqueous electrolyte battery and nonaqueous electrolyte battery |
| GB201909333D0 (en) * | 2019-06-28 | 2019-08-14 | Blackwood Benjamin | Decking board |
| WO2020091059A1 (en) * | 2018-11-01 | 2020-05-07 | 住友化学株式会社 | Nonaqueous electrolyte secondary battery |
| CN111164807A (en) * | 2017-09-29 | 2020-05-15 | Ａｔｔａｃｃａｔｏ合同会社 | Binder for lithium ion battery, and electrode and separator using same |
| CN111704425A (en) * | 2020-06-03 | 2020-09-25 | 武汉理工大学 | Calcium silicate board containing sepiolite clay minerals and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190393464A1 (en) * | 2017-12-12 | 2019-12-26 | Hollingsworth & Vose Company | Pasting papers and capacitance layers for batteries comprising multiple fiber types and/or particles |
-
2022
- 2022-09-22 CN CN202211157396.1A patent/CN115548575B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014123344A1 (en) * | 2013-02-06 | 2014-08-14 | Lee Jong-Hak | Natural substance area-enlarging uncoated natural wallpaper |
| CN108780914A (en) * | 2016-02-25 | 2018-11-09 | 旭化成株式会社 | Nonaqueous electrolyte battery inorganic particle and nonaqueous electrolyte battery |
| JP2018200795A (en) * | 2017-05-26 | 2018-12-20 | 旭化成株式会社 | Inorganic particles for nonaqueous electrolyte battery and nonaqueous electrolyte battery |
| CN111164807A (en) * | 2017-09-29 | 2020-05-15 | Ａｔｔａｃｃａｔｏ合同会社 | Binder for lithium ion battery, and electrode and separator using same |
| CN108046680A (en) * | 2017-12-01 | 2018-05-18 | 界首市森威保温建材有限公司 | The high-quality energy saving processing technology of expanded perlite thermal-nsulation plate |
| CN108232089A (en) * | 2018-01-05 | 2018-06-29 | 吉林大学 | A kind of lithium ion battery diatomite diaphragm and preparation method thereof |
| WO2020091059A1 (en) * | 2018-11-01 | 2020-05-07 | 住友化学株式会社 | Nonaqueous electrolyte secondary battery |
| GB201909333D0 (en) * | 2019-06-28 | 2019-08-14 | Blackwood Benjamin | Decking board |
| CN111704425A (en) * | 2020-06-03 | 2020-09-25 | 武汉理工大学 | Calcium silicate board containing sepiolite clay minerals and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115548575A (en) | 2022-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109065804B (en) | Water-based ceramic/PVDF (polyvinylidene fluoride) mixed coating slurry as well as preparation method and application thereof | |
| CN112290161B (en) | Ultralow-moisture ceramic-coated lithium ion battery diaphragm and preparation method thereof | |
| CN111509173A (en) | Functional coating diaphragm for lithium ion battery and preparation method thereof | |
| CN108281592A (en) | A kind of heat safe composite battery separator film and preparation method thereof | |
| CN107994183B (en) | Method for manufacturing composite coating diaphragm special for lithium battery | |
| CN112054149B (en) | Lithium ion battery composite diaphragm and preparation method thereof | |
| CN106450115A (en) | Inorganic coated bacterial cellulose porous thin film and preparation method thereof | |
| CN112216928A (en) | Modified composite heat-resistant lithium ion battery diaphragm and preparation method thereof | |
| CN111009665A (en) | Microporous layer, gas diffusion layer, preparation method and application thereof | |
| CN103236511A (en) | Preparation method of super-heat-resistant organic/inorganic composite film | |
| CN1314142C (en) | Method for preparing melting carbonate fuel cell membrane using water-based flow casting technique | |
| CN114976492B (en) | High-cohesiveness polymer composite coating diaphragm and preparation method thereof | |
| CN109411673A (en) | Lithium ion battery separator slurry and preparation method and lithium ion battery separator | |
| CN111477818B (en) | Full-ceramic lithium ion battery diaphragm and preparation method thereof | |
| CN113937419B (en) | Ceramic diaphragm based on organic-inorganic composite binder and preparation method thereof | |
| CN115548575B (en) | Baking-free all-inorganic lithium ion battery diaphragm and preparation method thereof | |
| CN113998933A (en) | Calcium silicate board and preparation method thereof | |
| CN112795247B (en) | High-viscosity PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof | |
| CN106531929A (en) | Drying process of ceramic coated bacterial cellulose porous thin film | |
| CN112751140B (en) | Diaphragm functional coating material for improving liquid retention capacity and safety performance of lithium ion battery electrolyte | |
| CN111477819B (en) | Full-ceramic diaphragm for lithium ion battery and preparation method thereof | |
| CN110627411B (en) | Ceramic slurry for high-temperature-resistant lithium ion battery diaphragm and application thereof | |
| CN114421091A (en) | Preparation method of lithium battery composite diaphragm with multilayer structure | |
| CN112421183A (en) | Method for continuously preparing lithium battery diaphragm by using melt spinning process | |
| CN112713362A (en) | Thermal buffer fiber modified diaphragm for lithium battery and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |