CN114050307B - High-performance lithium battery - Google Patents
High-performance lithium battery Download PDFInfo
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- CN114050307B CN114050307B CN202111363769.6A CN202111363769A CN114050307B CN 114050307 B CN114050307 B CN 114050307B CN 202111363769 A CN202111363769 A CN 202111363769A CN 114050307 B CN114050307 B CN 114050307B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 28
- -1 polyethylene Polymers 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 26
- 150000001336 alkenes Chemical class 0.000 claims description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000011256 inorganic filler Substances 0.000 claims description 22
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 18
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims description 16
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 16
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 239000012968 metallocene catalyst Substances 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 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 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 230000000149 penetrating effect Effects 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 229910001848 post-transition metal Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002457 bidirectional effect Effects 0.000 claims description 2
- 239000012934 organic peroxide initiator Substances 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims 2
- 238000005192 partition Methods 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical group COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 5
- 239000010954 inorganic particle Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 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
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to the technical field of lithium batteries, in particular to a high-performance lithium battery, which comprises a shell and a battery cell arranged in the shell, wherein an anode and a cathode are wound on the battery cell, a separator is arranged between the anode and the cathode, the separator comprises a carbon layer, a non-woven fabric layer wrapping the carbon layer, a ceramic material layer wrapping the surface of the non-woven fabric layer, and a diaphragm layer wrapping the surface of the ceramic material layer, and the diaphragm layer is made of a diaphragm material. The high-performance lithium battery has the advantages of high energy density, good multiplying power charge and discharge, long cycle life, safety and stability and high performance; the separator has the advantages of high puncture resistance and good fracture resistance by adopting a multi-layer wrapped structure, and improves the protection performance of the lithium battery separator to the battery.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a high-performance lithium battery.
Background
With the rapid development of electronic devices and the increasing prominence of energy and environmental problems, chemical power supplies are put on higher demands. The lithium ion battery has the advantages of high voltage, large specific energy, long cycle life, no pollution and the like, and rapidly grows in the market, thereby becoming a novel clean and high-energy source. In particular, in the twenty-first century, various portable electronic devices, wireless mobile communication devices, and electric vehicles have been rapidly developed and widely used, and the demand for lithium ion batteries with higher specific capacity, long cycle life and low cost has been urgent.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a high-performance lithium battery which has the advantages of high energy density, good multiplying power charge and discharge, long cycle life, safety and stability and high performance; the separator has the advantages of high puncture resistance and good fracture resistance by adopting a multi-layer wrapped structure, and improves the protection performance of the lithium battery separator to the battery.
The aim of the invention is achieved by the following technical scheme: the high-performance lithium battery comprises a shell and a battery cell arranged in the shell, wherein an anode and a cathode are wound on the battery cell, a separator is arranged between the anode and the cathode, the separator comprises a carbon layer, a non-woven fabric layer wrapped outside the carbon layer, a ceramic material layer wrapped on the surface of the non-woven fabric layer, and a diaphragm layer wrapped on the surface of the ceramic material layer, and the diaphragm layer is made of a diaphragm material; the ceramic material layer is a zirconia layer.
The high-performance lithium battery of the invention adopts the structure to greatly improve the charge and discharge performance of the coiled lithium battery, so that the lithium battery adopting the structure has the advantages of high energy density, good multiplying power charge and discharge, long cycle life, safety and stability and high performance; the separator has the advantages of high puncture resistance and good fracture resistance by adopting a multi-layer wrapped structure, improves the protection performance of the lithium battery separator to the battery, and also increases the electrolyte-philic performance, heat dissipation performance, mechanical strength and other performances of the separator.
Preferably, the separator is provided with micropores penetrating the separator layer and the ceramic material layer, and the diameter of the micropores is 0.020-0.030 μm.
The invention has the advantages that the pore size distribution of the micropores of the separator is uniform, the defect that the closed cell-shaped pore structure is easy to form in the preparation of the microporous separator by the traditional thermally induced phase separation method is overcome, the electrolyte-philic liquid of the separator is increased, and meanwhile, the separator is fully contacted with the electrolyte, so that the energy density of the high-performance lithium battery is obviously improved.
Preferably, the diaphragm material comprises the following raw materials in parts by weight: 4-8 parts of thermoplastic elastomer, 1-3 parts of pore-forming agent, 1-5 parts of N, N-dimethylformamide, 0.5-1.0 part of initiator, 20-40 parts of high molecular olefin, 1-3 parts of catalyst, 1-5 parts of inorganic filler and 2-6 parts of nano silicon carbide whisker; the thermoplastic elastomer is at least one of a styrene-butadiene-styrene block copolymer, an ethylene-vinyl acetate copolymer and an ethylene-vinyl alcohol copolymer.
The membrane material prepared from the raw materials has the characteristics of good mechanical property, interface hydrophilicity, high flame retardance, high heat resistance, high strength and high liquid absorption rate. The adopted macromolecular olefin base system is matched with a thermoplastic elastomer to be processed into a diaphragm, so that the affinity of the conventional polyethylene diaphragm to electrolyte can be improved, and the safety performance of the lithium battery is improved; meanwhile, the mechanical property of the manufactured diaphragm is ensured so as to adapt to machine winding and normal operation of the lithium battery during the assembly of the lithium battery; meanwhile, the nano silicon carbide whisker is added to improve the high-temperature shrinkage resistance and the tensile strength of the diaphragm material, so that the physical and chemical properties of the point battery diaphragm in the prior art are greatly improved; the hydrophilic pore-forming agent is introduced to replace the inorganic particle pore-forming agent, so that firstly, the problem of difficult dispersion of inorganic particles in an organic solvent is avoided, the uniformity of a coating and the uniformity of pore forming are improved, and secondly, the interface hydrophilicity between a diaphragm material and electrolyte is improved; in addition, the thermoplastic elastomer can also endow the diaphragm with good elasticity, and compared with the traditional polyolefin diaphragm, the diaphragm has the characteristics of high flame retardance, high heat resistance, high strength and high liquid absorption rate, the service performance and the safety performance of the lithium battery are greatly improved, and the preparation method is simple and can be applied to the field of forming and processing of high-end lithium battery diaphragms.
Preferably, the pore-forming agent is at least one of ethanol, propanol, isopropanol, polycaprolactone, polyvinyl alcohol, sodium polyacrylate and polyacrylamide. More preferably, the pore-forming agent is a mixture composed of isopropanol, polycaprolactone, polyvinyl alcohol and polyacrylamide according to the weight ratio of 0.6-1.0:0.8-1.2:0.4-0.8:0.1-0.5.
The specific pore-forming agent adopted in the invention replaces the prior inorganic particle pore-forming agent, firstly avoids the problem of difficult dispersion of inorganic particles in an organic solvent, improves the uniformity of coating and pore forming, secondly improves the interface hydrophilicity between a membrane material and electrolyte, and has the advantages of good connectivity, no blind holes and uniform pore size distribution of micropores of the prepared membrane material, overcomes the defect that the microporous membrane prepared by the traditional thermal phase separation method is easy to form a closed cell-shaped pore structure,
preferably, the high molecular olefin is a mixture composed of polyethylene, polypropylene and polytetrafluoroethylene according to the weight ratio of 0.6-1.0:0.8-1.2:0.4-0.8.
The polytetrafluoroethylene in the specific high molecular olefin adopted in the invention has better flexibility, cold resistance, tear resistance and puncture resistance, can comprehensively improve the mechanical strength of the diaphragm, and improves the low-temperature circularity, liquid retention and other characteristics of the component; and the adopted polypropylene and polytetrafluoroethylene have good electrophilic liquid, heat dissipation performance and mechanical strength, and can integrally improve the comprehensive performance of the diaphragm material.
Preferably, the initiator is an organic peroxide initiator or an azo initiator. More preferably, the initiator is cumene hydroperoxide or azobisisobutyronitrile.
Preferably, the catalyst is a metallocene catalyst or a late transition metal catalyst. More preferably, the metallocene catalyst is a metallocene polyethylene and the late transition metal catalyst is a SHOP catalyst manufactured by Shell company.
The catalyst of the specific type adopted in the invention is compounded, mixed or reacted with inorganic materials in the ethylene polymerization process to obtain single-active-center polyethylene with the weight average molecular weight of 20-50 ten thousand, and the catalyst has the characteristic of narrow molecular weight distribution.
Preferably, the inorganic filler is a mixture composed of calcium carbonate, montmorillonite, nano calcium carbonate and nano silicon carbide according to the weight ratio of 0.6-1.0:0.8-1.2:0.4-0.8:0.1-0.5.
The inorganic filler of the specific type adopted in the invention is tightly combined with the growing molecular chain in the polymerization process, so that the dispersity and uniformity of the pore-forming agent in the high molecular olefin raw material are greatly increased, meanwhile, the extremely good compatibility of the pore-forming agent with the polyethylene is further enhanced by carrying out surface modification on the inorganic material, the dispersion effect of the pore-forming agent in the high molecular olefin is ensured, and meanwhile, uniform and extremely small micropores can be obtained in hot stretching through the tiny difference of interfaces.
Preferably, the separator material is prepared by the steps of:
1) Adding a thermoplastic elastomer, high molecular olefin and an inorganic filler into a pulverizer according to parts by weight, pulverizing, and mixing with a pore-forming agent to prepare a mixture A for later use;
2) Adding N, N-dimethylformamide and nano silicon carbide whiskers into the mixture A obtained in the step 1) according to parts by weight, stirring uniformly, then sequentially adding an initiator and a catalyst, heating to 100-120 ℃ and stirring for 20-40min to obtain a mixture B for later use;
3) Putting the mixture B obtained in the step 2) into an extruder, casting through a die orifice, shaping by a cooling roller to prepare a casting film, and performing bidirectional/unidirectional stretching pore forming, film forming, slitting and rolling at 80-110 ℃ to obtain the diaphragm material.
The membrane material is prepared by the method, and the membrane material prepared by the method has the characteristics of good mechanical property, interface hydrophilicity, high flame retardance, high heat resistance, high strength and high liquid absorption. In the preparation process, a tape casting film is prepared by adopting a tape casting technology, mechanical strength is improved through bidirectional/unidirectional stretching, a microporous structure is formed through washing by a pore-forming agent, performance is further improved through heat setting, and finally a diaphragm material is obtained after winding.
The invention has the beneficial effects that: the high-performance lithium battery has the advantages of high energy density, good multiplying power charge and discharge, long cycle life, safety and stability and high performance; the separator has the advantages of high puncture resistance and good fracture resistance by adopting a multi-layer wrapped structure, and improves the protection performance of the lithium battery separator to the battery.
Drawings
Fig. 1 is a perspective view of the present invention.
Fig. 2 is a schematic cross-sectional structure of the separator of the present invention.
The reference numerals are: 1-shell, 2-cell, 21-baffle, 211-carbon layer, 212-non-woven fabric layer, 213-ceramic material layer and 214-diaphragm layer.
Detailed Description
The present invention is further described below with reference to examples and figures 1-2, which are not intended to be limiting, for the purpose of facilitating understanding of those skilled in the art.
Example 1
The high-performance lithium battery comprises a shell 1 and a battery cell 2 arranged in the shell 1, wherein an anode and a cathode are wound on the battery cell 2, a separator 21 is arranged between the anode and the cathode, the separator 21 comprises a carbon layer 211, a non-woven fabric layer 212 wrapping the carbon layer 211, a ceramic material layer 213 wrapping the surface of the non-woven fabric layer 212, and a diaphragm layer 214 wrapping the surface of the ceramic material layer 213, and the diaphragm layer 214 is made of diaphragm materials; the ceramic material layer 213 is a zirconia layer.
The separator 21 is provided with micropores penetrating the separator layer 214 and the ceramic material layer 213, the micropores having a diameter of 0.020 μm.
The diaphragm material comprises the following raw materials in parts by weight: 4 parts of thermoplastic elastomer, 1 part of pore-forming agent, 1 part of N, N-dimethylformamide, 0.5 part of initiator, 20 parts of high molecular olefin, 1 part of catalyst, 1 part of inorganic filler and 2 parts of nano silicon carbide whisker.
The pore-forming agent is a mixture composed of isopropanol, polycaprolactone, polyvinyl alcohol and polyacrylamide according to the weight ratio of 0.6:0.8:0.4:0.1. The high molecular olefin is a mixture composed of polyethylene, polypropylene and polytetrafluoroethylene according to the weight ratio of 0.6:0.8:0.4.
The initiator is cumene hydroperoxide.
The metallocene catalyst is metallocene polyethylene, and the post-transition metal catalyst is SHOP catalyst produced by Shell company.
The inorganic filler is a mixture composed of calcium carbonate, montmorillonite, nano calcium carbonate and nano silicon carbide according to the weight ratio of 0.6:0.8:0.4:0.1
The diaphragm material is prepared through the following steps:
1) Adding a thermoplastic elastomer, high molecular olefin and an inorganic filler into a pulverizer according to parts by weight, pulverizing, and mixing with a pore-forming agent to prepare a mixture A for later use;
2) Adding N, N-dimethylformamide and nano silicon carbide whiskers into the mixture A obtained in the step 1) according to parts by weight, stirring uniformly, then sequentially adding an initiator and a catalyst, heating to 100 ℃, and stirring for 20min to obtain a mixture B for later use;
3) Putting the mixture B obtained in the step 2) into an extruder, casting through a die orifice, shaping by a cooling roller to prepare a casting film, and performing bidirectional/unidirectional stretching pore forming, film forming, slitting and rolling at 80 ℃ to obtain the diaphragm material.
The thermoplastic elastomer is a styrene-butadiene-styrene block copolymer, and the styrene-butadiene-styrene block copolymer is YH-796SBS produced by Baling petrochemical industry.
Example 2
The high-performance lithium battery comprises a shell 1 and a battery cell 2 arranged in the shell 1, wherein an anode and a cathode are wound on the battery cell 2, a separator 21 is arranged between the anode and the cathode, the separator 21 comprises a carbon layer 211, a non-woven fabric layer 212 wrapping the carbon layer 211, a ceramic material layer 213 wrapping the surface of the non-woven fabric layer 212, and a diaphragm layer 214 wrapping the surface of the ceramic material layer 213, and the diaphragm layer 214 is made of diaphragm materials; the ceramic material layer 213 is a zirconia layer.
The separator 21 is provided with micropores penetrating the separator layer 214 and the ceramic material layer 213, the micropores having a diameter of 0.023 μm.
The diaphragm material comprises the following raw materials in parts by weight: 5 parts of thermoplastic elastomer, 1.5 parts of pore-forming agent, 1 part of N, N-dimethylformamide, 0.7 part of initiator, 25 parts of high molecular olefin, 1.5 parts of catalyst, 2 parts of inorganic filler and 3 parts of nano silicon carbide whisker.
The pore-forming agent is a mixture composed of isopropanol, polycaprolactone, polyvinyl alcohol and polyacrylamide according to the weight ratio of 0.7:0.9:0.5:0.2. The high molecular olefin is a mixture composed of polyethylene, polypropylene and polytetrafluoroethylene according to the weight ratio of 0.7:0.9:0.5.
The initiator is azobisisobutyronitrile.
The metallocene catalyst is metallocene polyethylene, and the post-transition metal catalyst is SHOP catalyst produced by Shell company.
The inorganic filler is a mixture composed of calcium carbonate, montmorillonite, nano calcium carbonate and nano silicon carbide according to the weight ratio of 0.7:0.9:0.5:0.2
The diaphragm material is prepared through the following steps:
1) Adding a thermoplastic elastomer, high molecular olefin and an inorganic filler into a pulverizer according to parts by weight, pulverizing, and mixing with a pore-forming agent to prepare a mixture A for later use;
2) Adding N, N-dimethylformamide and nano silicon carbide whiskers into the mixture A obtained in the step 1) according to parts by weight, stirring uniformly, then sequentially adding an initiator and a catalyst, heating to 105 ℃, and stirring for 25min to obtain a mixture B for later use;
3) Putting the mixture B obtained in the step 2) into an extruder, casting through a die orifice, shaping by a cooling roller to prepare a casting film, and performing bidirectional/unidirectional stretching pore forming, film forming, slitting and rolling at 87 ℃ to obtain the diaphragm material.
The thermoplastic elastomer is a styrene-butadiene-styrene block copolymer, and the styrene-butadiene-styrene block copolymer is YH-796SBS produced by Baling petrochemical industry.
Example 3
The high-performance lithium battery comprises a shell 1 and a battery cell 2 arranged in the shell 1, wherein an anode and a cathode are wound on the battery cell 2, a separator 21 is arranged between the anode and the cathode, the separator 21 comprises a carbon layer 211, a non-woven fabric layer 212 wrapping the carbon layer 211, a ceramic material layer 213 wrapping the surface of the non-woven fabric layer 212, and a diaphragm layer 214 wrapping the surface of the ceramic material layer 213, and the diaphragm layer 214 is made of diaphragm materials; the ceramic material layer 213 is a zirconia layer.
The separator 21 is provided with micropores penetrating the separator layer 214 and the ceramic material layer 213, the micropores having a diameter of 0.025 μm.
The diaphragm material comprises the following raw materials in parts by weight: 6 parts of thermoplastic elastomer, 2 parts of pore-forming agent, 3 parts of N, N-dimethylformamide, 0.8 part of initiator, 30 parts of high molecular olefin, 2 parts of catalyst, 3 parts of inorganic filler and 4 parts of nano silicon carbide whisker.
The pore-forming agent is a mixture composed of isopropanol, polycaprolactone, polyvinyl alcohol and polyacrylamide according to the weight ratio of 0.8:1.0:0.6:0.3. The high molecular olefin is a mixture composed of polyethylene, polypropylene and polytetrafluoroethylene according to the weight ratio of 0.8:1.0:0.6.
The initiator is cumene hydroperoxide.
The metallocene catalyst is metallocene polyethylene, and the post-transition metal catalyst is SHOP catalyst produced by Shell company.
The inorganic filler is a mixture composed of calcium carbonate, montmorillonite, nano calcium carbonate and nano silicon carbide according to the weight ratio of 0.8:1.0:0.6:0.3
The diaphragm material is prepared through the following steps:
1) Adding a thermoplastic elastomer, high molecular olefin and an inorganic filler into a pulverizer according to parts by weight, pulverizing, and mixing with a pore-forming agent to prepare a mixture A for later use;
2) Adding N, N-dimethylformamide and nano silicon carbide whiskers into the mixture A obtained in the step 1) according to parts by weight, stirring uniformly, then sequentially adding an initiator and a catalyst, heating to 110 ℃, and stirring for 30min to obtain a mixture B for later use;
3) Putting the mixture B obtained in the step 2) into an extruder, casting through a die orifice, shaping by a cooling roller to prepare a casting film, and performing bidirectional/unidirectional stretching pore forming, film forming, slitting and rolling at the temperature of 95 ℃ to obtain the diaphragm material.
The thermoplastic elastomer is a styrene-butadiene-styrene block copolymer, and the styrene-butadiene-styrene block copolymer is YH-796SBS produced by Baling petrochemical industry.
Example 4
The high-performance lithium battery comprises a shell 1 and a battery cell 2 arranged in the shell 1, wherein an anode and a cathode are wound on the battery cell 2, a separator 21 is arranged between the anode and the cathode, the separator 21 comprises a carbon layer 211, a non-woven fabric layer 212 wrapping the carbon layer 211, a ceramic material layer 213 wrapping the surface of the non-woven fabric layer 212, and a diaphragm layer 214 wrapping the surface of the ceramic material layer 213, and the diaphragm layer 214 is made of diaphragm materials; the ceramic material layer 213 is a zirconia layer.
The separator 21 is provided with micropores penetrating the separator layer 214 and the ceramic material layer 213, the micropores having a diameter of 0.027 μm.
The diaphragm material comprises the following raw materials in parts by weight: 7 parts of thermoplastic elastomer, 2.5 parts of pore-forming agent, 4 parts of N, N-dimethylformamide, 0.9 part of initiator, 35 parts of high molecular olefin, 2.5 parts of catalyst, 4 parts of inorganic filler and 5 parts of nano silicon carbide whisker.
The pore-forming agent is a mixture composed of isopropanol, polycaprolactone, polyvinyl alcohol and polyacrylamide according to the weight ratio of 0.9:1.1:0.7:0.4. The high molecular olefin is a mixture composed of polyethylene, polypropylene and polytetrafluoroethylene according to the weight ratio of 0.9:1.1:0.7.
The initiator is cumene hydroperoxide.
The metallocene catalyst is metallocene polyethylene, and the post-transition metal catalyst is SHOP catalyst produced by Shell company.
The inorganic filler is a mixture composed of calcium carbonate, montmorillonite, nano calcium carbonate and nano silicon carbide according to the weight ratio of 0.9:1.1:0.7:0.4
The diaphragm material is prepared through the following steps:
1) Adding a thermoplastic elastomer, high molecular olefin and an inorganic filler into a pulverizer according to parts by weight, pulverizing, and mixing with a pore-forming agent to prepare a mixture A for later use;
2) Adding N, N-dimethylformamide and nano silicon carbide whiskers into the mixture A obtained in the step 1) according to parts by weight, stirring uniformly, then sequentially adding an initiator and a catalyst, heating to 115 ℃, and stirring for 35min to obtain a mixture B for later use;
3) Putting the mixture B obtained in the step 2) into an extruder, casting through a die orifice, shaping by a cooling roller to prepare a casting film, and performing bidirectional/unidirectional stretching pore forming, film forming, slitting and rolling at 93 ℃ to obtain the diaphragm material.
The thermoplastic elastomer is a styrene-butadiene-styrene block copolymer, and the styrene-butadiene-styrene block copolymer is YH-796SBS produced by Baling petrochemical industry.
Example 5
The high-performance lithium battery comprises a shell 1 and a battery cell 2 arranged in the shell 1, wherein an anode and a cathode are wound on the battery cell 2, a separator 21 is arranged between the anode and the cathode, the separator 21 comprises a carbon layer 211, a non-woven fabric layer 212 wrapping the carbon layer 211, a ceramic material layer 213 wrapping the surface of the non-woven fabric layer 212, and a diaphragm layer 214 wrapping the surface of the ceramic material layer 213, and the diaphragm layer 214 is made of diaphragm materials; the ceramic material layer 213 is a zirconia layer.
The separator 21 is provided with micropores penetrating the separator layer 214 and the ceramic material layer 213, the micropores having a diameter of 0.030 μm.
The diaphragm material comprises the following raw materials in parts by weight: 8 parts of thermoplastic elastomer, 3 parts of pore-forming agent, 5 parts of N, N-dimethylformamide, 1.0 part of initiator, 40 parts of high molecular olefin, 3 parts of catalyst, 5 parts of inorganic filler and 6 parts of nano silicon carbide whisker.
The pore-forming agent is a mixture composed of isopropanol, polycaprolactone, polyvinyl alcohol and polyacrylamide according to the weight ratio of 1.0:1.2:0.8:0.5. The high molecular olefin is a mixture composed of polyethylene, polypropylene and polytetrafluoroethylene according to the weight ratio of 1.0:1.2:0.8.
The initiator is cumene hydroperoxide or azobisisobutyronitrile.
The metallocene catalyst is metallocene polyethylene, and the post-transition metal catalyst is SHOP catalyst produced by Shell company.
The inorganic filler is a mixture composed of calcium carbonate, montmorillonite, nano calcium carbonate and nano silicon carbide according to the weight ratio of 1.0:1.2:0.8:0.5
The diaphragm material is prepared through the following steps:
1) Adding a thermoplastic elastomer, high molecular olefin and an inorganic filler into a pulverizer according to parts by weight, pulverizing, and mixing with a pore-forming agent to prepare a mixture A for later use;
2) Adding N, N-dimethylformamide and nano silicon carbide whiskers into the mixture A obtained in the step 1) according to parts by weight, stirring uniformly, then sequentially adding an initiator and a catalyst, heating to 120 ℃, and stirring for 40min to obtain a mixture B for later use;
3) Putting the mixture B obtained in the step 2) into an extruder, casting through a die orifice, shaping by a cooling roller to prepare a casting film, and performing bidirectional/unidirectional stretching pore forming, film forming, slitting and rolling at 80-110 ℃ to obtain the diaphragm material.
The thermoplastic elastomer is a styrene-butadiene-styrene block copolymer, and the styrene-butadiene-styrene block copolymer is YH-796SBS produced by Baling petrochemical industry.
The separator materials prepared in examples 1, 3 and 5 were subjected to performance tests, and the test results are shown in table 1 below:
the porosity is tested according to the Archimedes drainage method, and the oil absorption time is tested under the same conditions with a 10mm 4mm product; pore size was measured according to (AutoPore IV 9500 (Micromeritics Instrument Corporation) for tensile strength: standard GB/T1040.3-2006 for puncture strength: standard GB/T21302-2007 for liquid absorption rate: mass m 0 Soaking in electrolyte (available from Shanghai Tongbo materials science Co., ltd.) for 2 hr, taking out, sucking the electrolyte on the surface of the membrane with filter paper, and weighing m 1 Calculate the liquid absorption k= [ (m) 1 -m 0 )/m 0 ]×100％。
TABLE 1
| Project | Example 1 | Example 3 | Example 5 | Commercial products |
| Liquid absorption (%) | 236 | 242 | 247 | 196 |
| Puncture strength (N) | 79.1 | 80.3 | 81.2 | 60.7 |
| Tensile Strength (MPa) | 75.2 | 78.5 | 77.6 | 56.6 |
| Void fraction (%) | 61.3 | 64.1 | 63.4 | 57.1 |
The comparison of the embodiment 1, the embodiment 3 and the embodiment 5 shows that the diaphragm material prepared by the invention has higher liquid absorption rate/void ratio, puncture strength and tensile strength, and the diaphragm for the lithium battery can obviously improve the comprehensive performance of the prepared lithium battery and has wide market prospect and application value.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (9)
1. A high performance lithium battery, characterized by: the battery cell comprises a shell and a battery cell arranged in the shell, wherein an anode and a cathode are wound on the battery cell, a partition plate is arranged between the anode and the cathode, the partition plate comprises a carbon layer, a non-woven fabric layer wrapped outside the carbon layer, a ceramic material layer wrapped on the surface of the non-woven fabric layer and a diaphragm layer wrapped on the surface of the ceramic material layer, and the diaphragm layer is made of diaphragm materials; the diaphragm material comprises the following raw materials in parts by weight: 4-8 parts of thermoplastic elastomer, 1-3 parts of pore-forming agent, 1-5 parts of N, N-dimethylformamide, 0.5-1.0 part of initiator, 20-40 parts of high molecular olefin, 1-3 parts of catalyst, 1-5 parts of inorganic filler and 2-6 parts of nano silicon carbide whisker.
2. The high performance lithium battery of claim 1, wherein: the separator is provided with micropores penetrating through the separator layer and the ceramic material layer, and the diameter of the micropores is 0.020-0.030 mu m.
3. The high performance lithium battery of claim 1, wherein: the ceramic material layer is a zirconia layer.
4. The high performance lithium battery of claim 1, wherein: the pore-forming agent is at least one of ethanol, propanol, isopropanol, polycaprolactone, polyvinyl alcohol, sodium polyacrylate and polyacrylamide.
5. The high performance lithium battery of claim 1, wherein: the high molecular olefin is a mixture composed of polyethylene, polypropylene and polytetrafluoroethylene according to the weight ratio of 0.6-1.0:0.8-1.2:0.4-0.8.
6. The high performance lithium battery of claim 1, wherein: the initiator is an organic peroxide initiator or an azo initiator.
7. The high performance lithium battery of claim 1, wherein: the catalyst is a metallocene catalyst or a post-transition metal catalyst.
8. The high performance lithium battery of claim 1, wherein: the inorganic filler is a mixture composed of calcium carbonate, montmorillonite, nano calcium carbonate and nano silicon carbide according to the weight ratio of 0.6-1.0:0.8-1.2:0.4-0.8:0.1-0.5.
9. A high performance lithium battery according to any one of claims 1-8, wherein: the diaphragm material is prepared through the following steps:
1) Adding a thermoplastic elastomer, high molecular olefin and an inorganic filler into a pulverizer according to parts by weight, pulverizing, and mixing with a pore-forming agent to prepare a mixture A for later use;
2) Adding N, N-dimethylformamide and nano silicon carbide whiskers into the mixture A obtained in the step 1) according to parts by weight, stirring uniformly, then sequentially adding an initiator and a catalyst, heating to 100-120 ℃ and stirring for 20-40min to obtain a mixture B for later use;
3) Putting the mixture B obtained in the step 2) into an extruder, casting through a die orifice, shaping by a cooling roller to prepare a casting film, and performing bidirectional/unidirectional stretching pore forming, film forming, slitting and rolling at 80-110 ℃ to obtain the diaphragm material.
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| JPS63175347A (en) * | 1987-01-16 | 1988-07-19 | Toshiba Corp | Nonaqueous solvent battery |
| JP2008027823A (en) * | 2006-07-25 | 2008-02-07 | Denso Corp | Sealing plate for battery container, method for manufacturing it, and nonaqueous electrolyte cell |
| KR20140082261A (en) * | 2012-12-24 | 2014-07-02 | 주식회사 엘지화학 | Tri-layered separator, electrochemical device comprising the same, and method of preparing the separator |
| CN105140455A (en) * | 2015-06-29 | 2015-12-09 | 柳州蚊敌香业有限公司 | Lithium battery module for electric vehicle |
| CN112670665A (en) * | 2020-12-23 | 2021-04-16 | 江苏厚生新能源科技有限公司 | High-performance lithium battery diaphragm and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS63175347A (en) * | 1987-01-16 | 1988-07-19 | Toshiba Corp | Nonaqueous solvent battery |
| JP2008027823A (en) * | 2006-07-25 | 2008-02-07 | Denso Corp | Sealing plate for battery container, method for manufacturing it, and nonaqueous electrolyte cell |
| KR20140082261A (en) * | 2012-12-24 | 2014-07-02 | 주식회사 엘지화학 | Tri-layered separator, electrochemical device comprising the same, and method of preparing the separator |
| CN105140455A (en) * | 2015-06-29 | 2015-12-09 | 柳州蚊敌香业有限公司 | Lithium battery module for electric vehicle |
| CN112670665A (en) * | 2020-12-23 | 2021-04-16 | 江苏厚生新能源科技有限公司 | High-performance lithium battery diaphragm and preparation method thereof |
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