CN114512706B - Lithium ion battery diaphragm slurry and lithium ion battery diaphragm - Google Patents
Lithium ion battery diaphragm slurry and lithium ion battery diaphragm Download PDFInfo
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- CN114512706B CN114512706B CN202111603930.2A CN202111603930A CN114512706B CN 114512706 B CN114512706 B CN 114512706B CN 202111603930 A CN202111603930 A CN 202111603930A CN 114512706 B CN114512706 B CN 114512706B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 70
- 239000002002 slurry Substances 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 21
- 229910010199 LiAl Inorganic materials 0.000 claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 43
- 239000006185 dispersion Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 239000011247 coating layer Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- 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)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a lithium ion battery diaphragm slurry, which comprises porous carboxylated graphene oxide and porous LiAl (SiO) 3 ) 2 Nanoparticles, a binder, and deionized water. The invention also discloses a preparation method of the lithium ion battery diaphragm slurry and a lithium ion battery diaphragm prepared by taking the lithium ion battery diaphragm slurry as a raw material. The diaphragm prepared from the lithium ion battery diaphragm slurry can not only effectively prevent the rapid diffusion of thermal runaway of the lithium ion battery and ensure the safety of the battery, but also improve the multiplying power and the cycle performance of the battery, and the preparation process is simple and easy to realize industrial production and application.
Description
Technical Field
The invention relates to the technical field of lithium ion battery diaphragm materials, in particular to lithium ion battery diaphragm slurry and a lithium ion battery diaphragm.
Background
The lithium ion battery diaphragm is one of four key materials of the lithium ion battery, is arranged between the positive electrode and the negative electrode of the battery, plays an isolating role in preventing the positive electrode and the negative electrode from being in contact with short circuit in the battery, simultaneously provides an ion transmission channel in the charge and discharge process, is a core component of the lithium ion battery, and the performance of the lithium ion battery diaphragm directly influences the capacity, the cycle performance and the safety performance of the battery. With the improvement of battery energy density and the increase of single cell capacity, the requirements on the consistency and the safety performance of batteries are also higher and higher. Among them, surface coating of polyolefin separator is an effective means for improving the consistency and safety performance of battery, and coating of alumina ceramic and PVDF gel layer on the surface of conventional separator by a certain process is a widely used means. As the material with the highest technical content and latest localization, the development of the domestic diaphragm plays a vital role in the development of the lithium ion battery in China.
Disclosure of Invention
Based on the technical problems existing in the background technology, the invention provides a lithium ion battery diaphragm slurry and a lithium ion battery diaphragm, which can enhance the diaphragm strength and the thermal fusing performance thereof, and simultaneously provide Li + Transfer channels and can supplement Li for electrolyte + 。
The invention provides a lithium ion battery diaphragm slurry, which comprises porous carboxylated graphene oxide and porous LiAl (SiO) 3 ) 2 The nanometer particle, the adhesive and deionized water, wherein the adhesive is polyacrylic acid, and the molecular formula is [ C ] 3 H 4 O 2 ]n。
Preferably, in the hole carboxylated graphene oxide, the mass of the oxygen element accounts for 30-45% of the total mass of the hole carboxylated graphene oxide, and the mass of the oxygen element in the carboxyl of the hole carboxylated graphene oxide accounts for 25-45% of the total mass of the oxygen element in the hole carboxylated graphene oxide.
In the invention, the porous carboxylated graphene oxide (GO-COOH) can be prepared by a conventional method, and specifically can be: performing conventional pore-forming treatment on the carboxylated graphene oxide to obtain the carboxylated graphene oxide with holes; or carboxylating the hole-carboxylated graphene oxide obtained through pore-forming treatment to obtain the hole-carboxylated graphene oxide.
In the invention, the pore-forming method is a conventional method, and concretely, the pore-forming method can be to adopt hydrogen peroxide for chemical etching treatment to form pores.
In the present invention, the carboxylation method is a conventional method, and concretely, carboxylation may be performed by chloroacetic acid treatment.
Preferably, the porous LiAl (SiO 3 ) 2 The D50 of the nanoparticle is 10-30nm.
In the present invention, porous LiAl (SiO 3 ) 2 The nano particles are prepared by taking spodumene ore as a raw material, purifying, calcining at high temperature, converting and ball milling; wherein the calcination temperature is 900-1200 ℃, and the ball milling method is a conventional method.
Preferably, in the formula of the binder, n is an integer of 45 to 65.
Preferably, the porous LiAl (SiO 3 ) 2 The mass ratio of the nano particles to the binder is (0.15-0.5): 1; the mass ratio of the binder to the porous carboxylated graphene oxide is (800-1500) 1.
Preferably, the solids content of the membrane slurry is 2-5%.
The preparation method of the lithium ion battery diaphragm slurry comprises the following steps:
s1, dispersing the hole carboxylated graphene oxide in a solvent to obtain a dispersion liquid I;
s2, adding a binder into the dispersion liquid I, and fully dissolving to obtain a dispersion liquid II;
s3, porous LiAl (SiO 3 ) 2 And adding the nano particles into the dispersion liquid II, and uniformly dispersing to obtain the lithium ion battery diaphragm slurry.
A lithium ion battery diaphragm comprises a base film and a coating layer positioned on at least one surface of the base film, wherein the coating layer is obtained by drying diaphragm slurry.
Preferably, the thickness of the coating layer is 0.4-0.8 μm.
The preparation method of the lithium ion battery diaphragm comprises the following steps: coating the membrane slurry on at least one surface of a base membrane, and drying at 70-90 ℃ for 2-3 hours to obtain the membrane.
The beneficial effects of the invention are as follows:
the invention adds the functional additive porous LiAl (SiO) into the formula of the diaphragm slurry 3 ) 2 Nanoparticles, porous knots thereofIs constructed as Li + Fast transfer provides a channel and absorbs H released when thermal runaway of the battery occurs 2 The method comprises the steps of carrying out a first treatment on the surface of the When the electrolyte undergoes side reaction to consume Li + When it is used, it can supplement Li to electrolyte + The method comprises the steps of carrying out a first treatment on the surface of the When the battery generates a great deal of heat in thermal runaway, the battery can quickly absorb heat and convert and release Al 2 O 3 And SiO 2 The protective base film prevents fusing; the porous carboxylated graphene oxide is added, so that the strength of the diaphragm can be increased, and more porous LiAl (SiO) 3 ) 2 Nanoparticles, and may be coated with thinner coatings; and [ C ] 3 H 4 O 2 ]The adhesive of n can strengthen the adhesive capacity of the porous GO-COOH and the base film through the hydrogen bond formed between the carboxyl in the adhesive and the carboxyl in the porous GO-COOH, so that the stability of the diaphragm is enhanced. The diaphragm slurry is used for preparing the lithium ion battery diaphragm, the prepared lithium ion battery diaphragm can effectively prevent the lithium ion battery from rapidly diffusing in thermal runaway, the safety of the battery is ensured, the multiplying power and the cycle performance of the battery can be improved, and the preparation process is simple and easy for large-scale preparation and production.
Drawings
Fig. 1 is a schematic structural diagram of a lithium ion battery separator according to the present invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
Preparing lithium ion battery diaphragm slurry:
dispersing 5g of the porous GO-COOH in deionized water to obtain a dispersion liquid I, wherein the mass of oxygen elements in the porous GO-COOH accounts for 30% of the total mass of the porous GO-COOH, and the mass of oxygen elements in carboxyl groups of the porous GO-COOH accounts for 25% of the total mass of oxygen elements in the porous GO-COOH; will be 4kg [ C 3 H 4 O 2 ] 45 Adding the mixture into the dispersion liquid I, and fully dissolving to obtain a dispersion liquid II; 800g of porous LiAl (SiO) with a D50 of 15nm 3 ) 2 And adding the nano particles into the dispersion liquid II, and stirring and dispersing uniformly to obtain the lithium ion battery diaphragm slurry with the solid content of 3%.
Preparing a lithium ion battery diaphragm:
and coating the lithium ion battery diaphragm slurry on one surface of a PE base film, and drying at 75 ℃ for 2.5h to form a coating layer of 0.4 mu m to obtain the lithium ion battery diaphragm.
Example 2
Preparing lithium ion battery diaphragm slurry:
dispersing 5g of the porous GO-COOH in deionized water to obtain a dispersion liquid I, wherein the mass of oxygen elements in the porous GO-COOH accounts for 35% of the total mass of the porous GO-COOH, and the mass of oxygen elements in carboxyl groups of the porous GO-COOH accounts for 30% of the total mass of oxygen elements in the porous GO-COOH; will 5kg [ C ] 3 H 4 O 2 ] 50 Adding the mixture into the dispersion liquid I, and fully dissolving to obtain a dispersion liquid II; 850g of porous LiAl (SiO) with a D50 of 20nm 3 ) 2 And adding the nano particles into the dispersion liquid II, and stirring and dispersing uniformly to obtain the lithium ion battery diaphragm slurry with the solid content of 3.2%.
Preparing a lithium ion battery diaphragm:
and coating the lithium ion battery diaphragm slurry on one surface of a PE base film, and drying at 75 ℃ for 2 hours to form a coating layer of 0.4 mu m, thereby obtaining the lithium ion battery diaphragm.
Example 3
Preparing lithium ion battery diaphragm slurry:
dispersing 5g of the porous GO-COOH in deionized water to obtain a dispersion liquid I, wherein the mass of oxygen elements in the porous GO-COOH accounts for 36% of the total mass of the porous GO-COOH, and the mass of oxygen elements in carboxyl groups of the porous GO-COOH accounts for 40% of the total mass of oxygen elements in the porous GO-COOH; will 5.5kg [ C ] 3 H 4 O 2 ] 50 Adding the mixture into the dispersion liquid I, and fully dissolving to obtain a dispersion liquid II; 1000g of porous LiAl (SiO) with a D50 of 20nm 3 ) 2 And adding the nano particles into the dispersion liquid II, and stirring and dispersing uniformly to obtain the lithium ion battery diaphragm slurry with the solid content of 3.5%.
Preparing a lithium ion battery diaphragm:
and coating the lithium ion battery diaphragm slurry on one surface of a PE base film, and drying at 80 ℃ for 2 hours to form a coating layer of 0.5 mu m, thereby obtaining the lithium ion battery diaphragm.
Example 4
Preparing lithium ion battery diaphragm slurry:
dispersing 5g of the porous GO-COOH in deionized water to obtain a dispersion liquid I, wherein the mass of oxygen elements in the porous GO-COOH accounts for 40% of the total mass of the porous GO-COOH, and the mass of oxygen elements in carboxyl groups of the porous GO-COOH accounts for 42% of the total mass of oxygen elements in the porous GO-COOH; 6kg [ C ] 3 H 4 O 2 ] 48 Adding the mixture into the dispersion liquid I, and fully dissolving to obtain a dispersion liquid II; 900g of porous LiAl (SiO) with a D50 of 25nm were reacted 3 ) 2 And adding the nano particles into the dispersion liquid II, and stirring and dispersing uniformly to obtain the lithium ion battery diaphragm slurry with the solid content of 4%.
Preparing a lithium ion battery diaphragm:
and coating the lithium ion battery diaphragm slurry on one surface of a PE base film, and drying at 80 ℃ for 2 hours to form a coating layer of 0.5 mu m, thereby obtaining the lithium ion battery diaphragm.
Example 5
Preparing lithium ion battery diaphragm slurry:
dispersing 5g of porous GO-COOH in deionized water to obtain a dispersion liquid I, wherein the mass of oxygen element in the porous GO-COOH accounts for 42% of the total mass of the porous GO-COOH, and the mass of oxygen element in carboxyl of the porous GO-COOH accounts for 40% of the total mass of oxygen element in the porous GO-COOH; will be 6.5kg [ C ] 3 H 4 O 2 ] 45 Adding the mixture into the dispersion liquid I, and fully dissolving to obtain a dispersion liquid II; 1300g of porous LiAl (SiO) with a D50 of 25nm were reacted 3 ) 2 And adding the nano particles into the dispersion liquid II, and stirring and dispersing uniformly to obtain the lithium ion battery diaphragm slurry with the solid content of 4.5%.
Preparing a lithium ion battery diaphragm:
and coating the lithium ion battery diaphragm slurry on one surface of a PE base film, and drying at 85 ℃ for 2.5h to form a coating layer of 0.8 mu m to obtain the lithium ion battery diaphragm.
Example 6
Preparing lithium ion battery diaphragm slurry:
dispersing 5g of porous GO-COOH in deionized water to obtain a dispersion liquid I, wherein the mass of oxygen element in the porous GO-COOH accounts for 45% of the total mass of the porous GO-COOH, and the mass of oxygen element in carboxyl of the porous GO-COOH accounts for 44% of the total mass of oxygen element in the porous GO-COOH; 7kg [ C ] 3 H 4 O 2 ] 45 Adding the mixture into the dispersion liquid I, and fully dissolving to obtain a dispersion liquid II; 1400g of porous LiAl (SiO) with a D50 of 28nm were reacted 3 ) 2 And adding the nano particles into the dispersion liquid II, and stirring and dispersing uniformly to obtain the lithium ion battery diaphragm slurry with the solid content of 5%.
Preparing a lithium ion battery diaphragm:
and coating the lithium ion battery diaphragm slurry on one surface of a PE base film, and drying at 70 ℃ for 2 hours to form a coating layer of 0.4 mu m, thereby obtaining the lithium ion battery diaphragm.
Comparative example
Adding 50g of alumina ceramic powder (d50=30-50 nm) into 15kg of NMP, and uniformly dispersing to obtain a first solution; 600g P (VDF-HFP) powder was added to 5kg NMP and dissolved with sufficient agitation to give a second solution; and mixing the first solution and the second solution, uniformly stirring, coating on one surface of the PE diaphragm, and drying to form a coating layer with the thickness of 2 mu m to obtain the lithium ion battery diaphragm.
The diaphragms prepared in the examples 1-6 and the comparative example are respectively assembled with a commercially available PP base film and a PE base film to form a lithium ion battery, and positive and negative electrode materials, electrolyte and designs are kept consistent, so that the full battery with the same specification and model is obtained. Performing a test on the performance of the battery, wherein the test method of the thermal runaway temperature refers to GB38031-2020, and the test condition of the 1500-week capacity retention rate is 1C@RT; the test results are shown in table 1:
TABLE 1
| Numbering device | Thermal runaway temperature/. Degree.C | 3C discharge capacity retention rate/% | Capacity retention at 1500 weeks/% |
| Example 1 | 316 | 95.60％ | 91.30％ |
| Example 2 | 317 | 95.70％ | 91.50％ |
| Example 3 | 315 | 96.20％ | 90.90％ |
| Example 4 | 319 | 95.90％ | 91.20％ |
| Example 5 | 318 | 96.30％ | 90.80％ |
| Example 6 | 320 | 96.10％ | 91.40％ |
| Comparative example | 210 | 82.30％ | 80.20％ |
| PP base film | 150 | 82.40％ | 80.40％ |
| PE base film | 120 | 82.20％ | 80.50％ |
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. The lithium ion battery diaphragm is characterized by comprising a base film and a coating layer positioned on at least one surface of the base film, wherein the coating layer is obtained by drying diaphragm slurry; the membrane slurry comprises porous carboxylated graphene oxide, porous LiAl (SiO 3 ) 2 Nanoparticles, a binder and deionized water, wherein the molecular formula of the binder is [ C ] 3 H 4 O 2 ]n；
The porous LiAl (SiO 3 ) 2 The mass ratio of the nano particles to the binder is (0.15-0.5): 1; the binder and the porous carboxylated graphene oxideThe mass ratio is (800-1500) 1.
2. The lithium ion battery separator according to claim 1, wherein in the hole carboxylated graphene oxide, the mass of oxygen element accounts for 30-45% of the total mass of the hole carboxylated graphene oxide, and the mass of oxygen element in the carboxyl group of the hole carboxylated graphene oxide accounts for 25-45% of the total mass of oxygen element in the hole carboxylated graphene oxide.
3. The lithium ion battery separator of claim 1, wherein the porous LiAl (SiO 3 ) 2 The D50 of the nanoparticle is 10-30nm.
4. The lithium ion battery separator of claim 1, wherein n is an integer from 45 to 65 in the molecular formula of the binder.
5. The lithium ion battery separator of claim 1, wherein the separator slurry has a solids content of 2-5%.
6. The lithium ion battery separator according to claim 1, wherein the preparation method of the separator slurry comprises the following steps:
s1, dispersing the hole carboxylated graphene oxide in a solvent to obtain a dispersion liquid I;
s2, adding a binder into the dispersion liquid I, and fully dissolving to obtain a dispersion liquid II;
s3, porous LiAl (SiO 3 ) 2 And adding the nano particles into the dispersion liquid II, and uniformly dispersing to obtain the lithium ion battery diaphragm slurry.
7. The lithium ion battery separator according to claim 1, wherein the thickness of the coating layer is 0.4-0.8 μm.
8. A method of making a lithium ion battery separator according to claim 1, comprising: coating the membrane slurry on at least one surface of a base membrane, and drying at 70-90 ℃ for 2-3 hours to obtain the membrane.
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Citations (11)
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| CN112582749A (en) * | 2020-12-11 | 2021-03-30 | 重庆金美新材料科技有限公司 | Safe lithium ion battery diaphragm, preparation method and lithium ion battery |
| WO2021225831A1 (en) * | 2020-05-04 | 2021-11-11 | Soelect Inc. | Advanced solid electrolyte membranes and batteries made therefrom |
| CN113725555A (en) * | 2021-09-28 | 2021-11-30 | 星恒电源(滁州)有限公司 | Lithium ion battery diaphragm and preparation method thereof |
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| US9287540B2 (en) * | 2011-05-31 | 2016-03-15 | GM Global Technology Operations LLC | Separators for a lithium ion battery |
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| CN102810657A (en) * | 2011-05-31 | 2012-12-05 | 通用汽车环球科技运作有限责任公司 | Method for producing lithium ion battery separator |
| JP2013056825A (en) * | 2012-10-17 | 2013-03-28 | Ngk Insulators Ltd | Honeycomb structure |
| CN105514482A (en) * | 2016-01-29 | 2016-04-20 | 中南大学 | Preparation method of functional diaphragm of lithium sulfur battery |
| CN111630688A (en) * | 2018-02-01 | 2020-09-04 | 英国热陶瓷有限公司 | Energy storage device and ion-conductive composition used therein |
| CN108550762A (en) * | 2018-03-15 | 2018-09-18 | 桑顿新能源科技有限公司 | A kind of coating diaphragm of ternary lithium ion battery and preparation method thereof |
| CN110391087A (en) * | 2019-07-24 | 2019-10-29 | 湖南工业大学 | A kind of preparation method and applications of three kinds of element doping porous oxidation grapheme materials of nitrogen sulphur phosphorus |
| CN110690435A (en) * | 2019-10-17 | 2020-01-14 | 中南大学 | Fast ion conductor coated high-nickel ternary positive electrode material and preparation method thereof |
| WO2021225831A1 (en) * | 2020-05-04 | 2021-11-11 | Soelect Inc. | Advanced solid electrolyte membranes and batteries made therefrom |
| CN111769242A (en) * | 2020-06-23 | 2020-10-13 | 合肥国轩高科动力能源有限公司 | Diaphragm coating slurry capable of improving safety performance of lithium ion battery and preparation method thereof |
| CN112582749A (en) * | 2020-12-11 | 2021-03-30 | 重庆金美新材料科技有限公司 | Safe lithium ion battery diaphragm, preparation method and lithium ion battery |
| CN113725555A (en) * | 2021-09-28 | 2021-11-30 | 星恒电源(滁州)有限公司 | Lithium ion battery diaphragm and preparation method thereof |
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