CN117736388B - Porous buffer material, secondary battery and preparation method of secondary battery - Google Patents

Porous buffer material, secondary battery and preparation method of secondary battery Download PDF

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CN117736388B
CN117736388B CN202410191383.9A CN202410191383A CN117736388B CN 117736388 B CN117736388 B CN 117736388B CN 202410191383 A CN202410191383 A CN 202410191383A CN 117736388 B CN117736388 B CN 117736388B
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secondary battery
weight
parts
precursor dispersion
buffer material
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CN117736388A (en
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赵翔
崔屹
刘婵
侯敏
曹辉
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Shanghai Ruipu Energy Co Ltd
Rept Battero Energy Co Ltd
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Shanghai Ruipu Energy Co Ltd
Rept Battero Energy Co Ltd
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    • 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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Abstract

The invention provides a porous buffer material, a secondary battery and a preparation method thereof, wherein the porous buffer material is obtained by polymerizing precursor dispersion liquid, and the precursor dispersion liquid comprises a polymerized monomer, metal salt, an initiator, a foaming agent, a getter material, a heat insulation material, a flame retardant additive and an organic solvent; the components are matched, so that the porous buffer material obtained after the precursor dispersion liquid is polymerized has excellent heat insulation performance, liquid retention performance and air suction performance, and can be further applied to a secondary battery to effectively improve the liquid retention capacity of the battery core and absorb active gas released by the battery core, so that the secondary battery can be maintained to have higher electrochemical performance and simultaneously inhibit the aggravation of early thermal runaway, and the safety performance and the electrochemical performance of the secondary battery are effectively improved.

Description

Porous buffer material, secondary battery and preparation method of secondary battery
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a porous buffer material, a secondary battery and a preparation method of the secondary battery.
Background
Since commercialization, secondary batteries have changed the aspects of the world from aspects, and the development of energy storage systems, smart grids and electric vehicles is in need of further improving the energy density of the batteries; however, the energy density and safety are like the two ends of a teeterboard, and the chemical system of the high-nickel ternary anode and the high-silicon cathode with high specific capacity can improve the energy density of the battery, but also can obviously reduce the thermal safety of the battery, and a series of severe chain reactions can be initiated when the battery is out of control, so that the battery is ignited or even exploded.
At present, a solid-state battery using an all-solid electrolyte is considered as an ultimate solution to solve the problem of thermal safety, a ceramic oxide or sulfide solid-state electrolyte is not easy to burn, and a flammable polyethylene/polypropylene separator and an organic electrolyte are not contained in the battery, but the solid-state battery also has factors such as incompatibility of an electrode/electrolyte interface, large impedance, complex process, high cost and the like, so that the difficulty of commercialization application is high. In summary, the electrolyte of the secondary battery is mainly in a liquid form, and even in a semi-solid battery using a gel electrolyte, a large amount of organic electrolyte is still contained in the electrolyte.
Therefore, in order to solve the above-mentioned technical problems, it is highly desirable to develop a porous buffer material that can effectively improve the safety performance of the secondary battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a porous buffer material, a secondary battery and a preparation method thereof, wherein the porous buffer material has excellent heat insulation performance, liquid retention performance and air suction performance, and is coated on the surface of a pole core of the secondary battery when the porous buffer material is applied, so that the higher electrochemical performance of the secondary battery can be maintained, and the aggravation of early thermal runaway of the secondary battery can be restrained, and the safety performance and the cycle performance of the secondary battery are effectively improved.
To achieve the purpose, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a porous cushioning material obtained by polymerizing a precursor dispersion comprising a polymeric monomer, a metal salt, an initiator, a blowing agent, a getter material, a thermal insulation material, a flame retardant additive, and an organic solvent.
At present, in the production flow of commercial secondary batteries, a secondary liquid injection step is added after negative pressure formation so as to effectively improve the liquid retention capacity of the secondary batteries, and in general, the primary liquid injection and the secondary liquid injection are both commercial electrolyte and have the same formula; however, the inventor of the invention researches that the electrolyte of the secondary injection is replaced by the precursor dispersion liquid of the porous buffer material provided by the invention, and the precursor dispersion liquid specifically comprises a polymerized monomer, lithium salt, an initiator, a foaming agent, a getter material, a heat insulation material, a flame retardant additive and an organic solvent, wherein the precursor dispersion liquid can generate a buffer layer on the surface of a pole core after polymerization reaction, and the buffer layer can play roles of supplementing lithium salt to the pole core, absorbing active gas and blocking external high temperature, so that the thermal safety of the secondary battery is effectively improved on the premise of not influencing the electrochemical performance of the secondary battery;
Specifically, the polymerized monomer in the precursor dispersion liquid can generate a semi-solid gel state substance under the action of an initiator, the foaming agent can change the gel state substance into a porous structure, so that the heat insulation effect of the gel state substance is enhanced, and when the secondary battery is subjected to early thermal runaway, the porous structure is favorable for the absorption of active gas, the active gas can be fully absorbed by matching with the getter material, so that the thermal safety performance of the secondary battery is improved, the heat insulation material can be filled in the pores of the gel state material, the heat conductivity coefficient of the porous gel state substance is further reduced, the effect of the porous buffer material on blocking external high temperature influence is enhanced, and the metal salt can flow into the electrode core from the interface of the porous buffer material and the electrolyte adsorbed in the electrode core, so that the effect of maintaining internal secondary conduction of the electrode core is achieved, and the higher electrochemical performance is maintained.
Preferably, the precursor dispersion liquid comprises the following components in parts by weight:
1 part by weight of a polymerized monomer;
0.1-0.5 parts by weight of metal salt;
0.0005-0.4 parts by weight of an initiator;
0.01-0.2 parts by weight of a foaming agent;
0.1-0.5 parts by weight of a getter material;
0.1-0.5 parts by weight of a heat insulating material;
0.1-0.5 parts by weight of a flame retardant additive;
and 0.1-5 parts by weight of an organic solvent.
Wherein the metal salt may be 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, or the like.
The initiator may be 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, or the like.
The foaming agent may be 0.05 parts by weight, 0.1 parts by weight, 0.15 parts by weight, or the like.
The getter material may be 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, or 0.45 parts by weight, etc.
The heat insulating material may be 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, or the like.
The flame retardant additive may be 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, or the like.
The organic solvent may be 0.1 to 5 parts by weight, for example, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or the like.
Preferably, the foaming agent comprises any one or a combination of at least two of N, N' -dinitroso pentamethylene tetramine, ethylene glycol and glycerol.
Preferably, the getter material comprises a molecular sieve.
Preferably, the molecular sieve comprises any one or a combination of at least two of a 3A type molecular sieve, a 4A type molecular sieve, a 5A type molecular sieve, a 10X type molecular sieve and a 13X type molecular sieve.
Preferably, the thermal insulation material comprises silica aerogel.
Preferably, the particle size of the getter material and the heat insulator is each independently 0.1 to 150 μm, for example 0.5 μm, 1 μm, 5 μm, 10 μm, 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, 120 μm or 140 μm, etc.
Preferably, the polymeric monomer is a vinyl-containing monomer.
Preferably, the vinyl-containing monomer includes any one or a combination of at least two of n-butyl acrylate, isobutyl acrylate, propyl acrylate, polyethylene glycol methacrylate, polyethylene glycol monomethyl ether methacrylate, 2-methoxyethyl acrylate, ethyl acrylate, hexyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, n-octyl methacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, triethylene glycol diacrylate, glycidyl methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, gamma-methacryloxypropyl trimethoxysilane, allyl diethyl phosphate, bis (2-chloroethyl) vinyl phosphate, and allyl biphenyl phosphine oxide.
Preferably, the initiator comprises a peroxide initiator and/or an azo compound initiator.
Preferably, the initiator comprises an azo compound initiator, the azo compound initiator also has a certain foaming effect, and the azo compound initiator can be used as the initiator to produce a synergistic effect with a foaming agent, so that the porosity of the porous buffer material can be further increased.
Preferably, the peroxide initiator comprises benzoyl peroxide.
Preferably, the azo compound initiator comprises any one or a combination of at least two of azobisisobutyronitrile, dimethyl azobisisobutyrate, azodicarbonamide or azodiisoheptanenitrile.
Preferably, the metal salt comprises a lithium salt or a sodium salt.
In the present invention, the type of the lithium salt is not particularly limited, and the electrolyte lithium salt of a conventional secondary battery may be selected, and any one or a combination of at least two of lithium hexafluorophosphate, lithium bistrifluoro-methanesulfonimide, lithium bistrifluoro-sulfimide, lithium tetrafluoroborate, lithium difluorooxalato-borate, and lithium bisoxalato-borate is preferable.
In the present invention, the type of the sodium salt is not particularly limited, and the electrolyte sodium salt of a conventional secondary battery may be selected, and any one or a combination of at least two of sodium hexafluorophosphate, sodium bistrifluoro-methanesulfonimide, sodium bistrifluoro-sulfimide, sodium tetrafluoroborate, sodium difluoro-oxalato-borate and sodium bisoxalato-borate is preferable.
Preferably, the organic solvent comprises a phosphorus-containing organic solvent and/or a halogen-containing organic solvent; the phosphorus-containing organic solvent and/or the halogen-containing organic solvent are not easy to burn, so that the obtained porous buffer material has excellent flame retardant property.
Preferably, the phosphorus-containing organic solvent includes any one or a combination of at least two of trimethyl phosphate, triethyl phosphate, tributyl phosphate, toluene diphenyl phosphate, t-butyl triphenyl phosphate, tris (2, 6-xylyl) phosphate, resorcinol bis (diphenyl phosphate), bisphenol a bis (diphenyl phosphate), dimethyl methylphosphonate, diethyl phosphate, phenyl diphenyl 4-isopropyl phosphate, diphenyl octyl phosphate, tris (beta-chloroethyl) phosphate, or trioctyl phosphate.
Preferably, the halogen-containing organic solvent comprises any one or a combination of at least two of 1, 3-hexafluoroisopropyl methyl ether, perfluorobutyl methyl ether, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, fluoroethylene carbonate, propylene trifluorocarbonate, chloroethylene carbonate, methyl difluoroacetate or ethyl difluoroacetate.
Preferably, the flame retardant additive comprises any one or a combination of at least two of hexamethoxyphosphazene, bis (methoxyethoxyethoxy) phosphazene, hexaethoxyphosphazene, 4-methoxy-phenoxy pentafluoroethylene triphosphazene, decabromodiphenyl ether, tetrabromobisphenol a, or tetrabromobisphenol a bis (2.3-dibromopropyl) ether (octabromoether).
Preferably, the reaction temperature of the polymerization is 30 to 60 ℃, for example 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, or the like.
Preferably, the polymerization reaction time is 10-48 hours, such as 15 h, 20 h, 25 h, 30 h, 35 h, 40 h or 45 h, etc.
In a second aspect, the present invention provides a secondary battery comprising the porous cushioning material according to the first aspect, wherein the porous cushioning material is coated on the surface of the electrode core of the secondary battery.
In a third aspect, the present invention provides a method for producing the secondary battery according to the second aspect, the method comprising: and firstly injecting electrolyte into the battery core of the secondary battery, then injecting the precursor dispersion liquid of the porous buffer material, and polymerizing to obtain the secondary battery.
In the preparation method of the secondary battery provided by the invention, firstly, electrolyte is injected into a battery core of the secondary battery, so that a positive electrode plate, a diaphragm and a negative electrode plate of the secondary battery are fully soaked, then, precursor dispersion liquid is injected into the secondary battery, the precursor dispersion liquid is positioned between a pole core (comprising the positive electrode plate, the negative electrode plate and the diaphragm) and a battery shell, and finally, a layer of porous buffer material is uniformly coated on the surface of the pole core through polymerization, so that the secondary battery is obtained.
It should be noted that, since the electrode core is sufficiently impregnated with the electrolyte before the precursor dispersion liquid is injected, the precursor dispersion liquid injected subsequently does not infiltrate into the inside of the electrode core, and in order to further avoid the precursor dispersion liquid injected into the inside of the electrode core, it is necessary to complete the subsequent steps as soon as possible after the injection of the liquid, and at the same time, even if a small amount of precursor dispersion liquid infiltrates into the inside of the electrode core, the normal use of the obtained secondary battery is not affected.
Preferably, the total injection amount of the electrolyte and the precursor dispersion is 1.0-3.0 g/Ah, for example 1.5 g/Ah, 2 g/Ah, 2.5 g/Ah or 3 g/Ah, etc.
Preferably, the mass ratio of the injection amount of the electrolyte to the injection amount of the precursor dispersion is (5-20): 1, for example, 7:1, 9:1, 11:1, 13:1, 15:1, 17:1, 19:1, or the like.
Preferably, the electrolyte injection further comprises a step of aging and negative pressure formation.
Preferably, the temperature of the primary aging is 25-50 ℃, such as 30 ℃, 35 ℃, 40 ℃, 45 ℃ or the like.
Preferably, the time of the one aging is 10 to 30 hours, for example, 12 h, 14 h, 16h, 18 h, 20h, 22 h, 24h, 26 h or 28 h, etc.
Preferably, the vacuum degree of the negative pressure formation is-75 to-90 kPa, such as-80 kPa or-85 kPa.
Preferably, the step of injecting the precursor dispersion further includes a secondary aging step during which the secondary battery may be oscillated, turned over, or rotated.
Preferably, the temperature of the secondary aging is 20-25 ℃, such as 21 ℃, 22 ℃, 23 ℃ or 24 ℃.
Preferably, the secondary aging time is 10-30 hours, such as 12 h, 14 h, 16h, 18 h, 20h, 22 h, 24h, 26 h or 28 h.
Preferably, the polymerization reaction temperature is 30 to 60 ℃, for example 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, or the like.
Preferably, the polymerization reaction time is 10-48 hours, such as 15 h, 20 h, 25 h, 30 h, 35 h, 40 h or 45 h, etc.
Compared with the prior art, the invention has the following beneficial effects:
The porous buffer material is obtained by polymerizing a precursor dispersion liquid, wherein the precursor dispersion liquid comprises a polymerization monomer, metal salt, an initiator, a foaming agent, a getter material, a heat insulation material, a flame retardant additive and an organic solvent; the components are matched, so that the porous buffer material obtained after the precursor dispersion liquid is polymerized has excellent heat insulation performance, liquid retention performance and air suction performance, and can be further applied to a secondary battery to effectively improve the liquid retention capacity of the battery core and absorb active gas released by the battery core, so that the secondary battery can be maintained to have higher electrochemical performance and simultaneously inhibit the aggravation of early thermal runaway, and the safety performance and the electrochemical performance of the secondary battery are effectively improved.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The raw materials related to the specific embodiment are conventional and commercially available products unless otherwise specified;
polyethylene glycol methacrylate: the number average molecular weight was 550, purchased from Shanghai Ala Biotechnology Co., ltd;
type 4A molecular sieve: particle size of about 100 μm, available from Shanghai Ala Biotechnology Co., ltd;
Silica aerogel: the particle size was about 50 μm and the model AG-D aerogel powder was purchased from midget technologies Co.
Example 1
A porous buffer material obtained by polymerizing 48 h at 50 ℃ from a precursor dispersion;
The precursor dispersion liquid comprises the following components in parts by weight:
polyethylene glycol methacrylate 1 part by weight;
1 part by weight of trimethyl phosphate;
0.2 parts by weight of phenoxy pentafluoroethylphosphazene;
0.3 parts by weight of lithium hexafluorophosphate;
0.3 parts by weight of a 4A molecular sieve;
0.2 parts by weight of azodicarbonamide;
0.1 part by weight of N, N' -dinitroso pentamethylene tetramine;
0.3 parts by weight of silica aerogel;
The preparation method of the precursor dispersion liquid comprises the following steps: adding polyethylene glycol methacrylate, trimethyl phosphate, phenoxy pentafluoroethylene triphosphazene and lithium hexafluorophosphate into a reaction vessel in an environment with humidity less than 5% and temperature of 25 ℃ and stirring to a clear solution state, then heating the solution to 300 ℃ and cooling to 100 ℃, adding a type 4A molecular sieve into the solution, and then adding azodicarbonamide, N' -dinitroso pentamethylene tetramine and silicon dioxide aerogel and fully stirring for 1 h to obtain the precursor dispersion liquid.
Example 2
A porous buffer material obtained by polymerizing a precursor dispersion at 60 ℃ for 12 h;
The precursor dispersion liquid comprises the following components in parts by weight:
1 part by weight of n-butyl acrylate;
0.1 parts by weight of triethyl phosphate;
0.1 parts by weight of bis (methoxyethoxyethoxy) phosphazene;
0.1 parts by weight of lithium tetrafluoroborate;
0.1 part by weight of a 4A molecular sieve;
0.0005 parts by weight of dimethyl azodiisobutyrate;
0.01 part by weight of ethylene glycol;
0.1 parts by weight of silica aerogel;
the preparation method of the precursor dispersion liquid comprises the following steps: n-butyl acrylate, triethyl phosphate, bis (methoxyethoxyethoxy) phosphazene and lithium tetrafluoroborate are added to a reaction vessel in an environment with a humidity of < 5% and a temperature of 25 ℃ and stirred to a clear solution state, then a type 4A molecular sieve is added to the solution after the solution is heated to 300 ℃ and cooled to 100 ℃, and then dimethyl azodiisobutyrate, ethylene glycol and silica aerogel are added and sufficiently stirred for 1h to obtain the precursor dispersion.
Example 3
A porous buffer material obtained by polymerizing 48 h at 35 ℃ from a precursor dispersion;
The precursor dispersion liquid comprises the following components in parts by weight:
1 part by weight of ethylene glycol dimethacrylate;
5 parts by weight of 1, 3-hexafluoroisopropyl methyl ether;
0.5 parts by weight of phenoxy pentafluoroethylphosphazene;
0.5 parts by weight of lithium difluorooxalato borate;
0.5 parts by weight of a 4A molecular sieve;
0.4 parts by weight of azobisisoheptonitrile;
0.2 parts by weight of glycerol;
0.5 parts by weight of silica aerogel;
The preparation method of the precursor dispersion liquid comprises the following steps: ethylene glycol dimethacrylate, 1, 3-hexafluoroisopropyl methyl ether, phenoxy pentafluoroethylphosphazene and lithium difluorooxalate borate are added into a reaction vessel in an environment with humidity of less than 5% and temperature of 25 ℃ and stirred to a clear solution state, then a type 4A molecular sieve is added into the solution after the solution is heated to 300 ℃ and cooled to 100 ℃, and then azodiisoheptonitrile, glycerol and silica aerogel are added and fully stirred for 1h, so that the precursor dispersion liquid is obtained.
Example 4
A porous buffer material was distinguished from example 1 in that the lithium hexafluorophosphate in the precursor dispersion was replaced with an equal weight of sodium hexafluorophosphate, and the other components and amounts were the same as in example 1.
Example 5
A porous cushioning material was different from example 1 in that N, N' -dinitroso pentamethylene tetramine was added in an amount of 0.005 parts by weight to the precursor dispersion, and the other components and amounts were the same as in example 1.
Example 6
A porous cushioning material was different from example 1 in that N, N' -dinitroso pentamethylene tetramine was added in an amount of 0.4 parts by weight to the precursor dispersion, and the other components and amounts were the same as in example 1.
Example 7
A porous buffer material was different from example 1 in that the amount of the 4A type molecular sieve added to the precursor dispersion was 0.05 parts by weight, and the other components and amounts were the same as in example 1.
Example 8
A porous buffer material was different from example 1 in that the amount of the 4A type molecular sieve added to the precursor dispersion was 0.8 parts by weight, and the other components and amounts were the same as in example 1.
Example 9
A porous cushioning material was different from example 1 in that the silica aerogel was added in an amount of 0.05 parts by weight to the precursor dispersion, and the other components and amounts were the same as in example 1.
Example 10
A porous cushioning material was different from example 1 in that the silica aerogel was added in an amount of 0.8 parts by weight to the precursor dispersion, and the other components and amounts were the same as in example 1.
Comparative example 1
A porous cushioning material was different from example 1 in that N, N' -dinitroso pentamethylene tetramine was not added to the precursor dispersion liquid, and the other components and amounts were the same as in example 1.
Comparative example 2
A porous buffer material was different from example 1 in that no type 4A molecular sieve was added to the precursor dispersion, and the other components and amounts were the same as in example 1.
Comparative example 3
A porous cushioning material was different from example 1 in that silica aerogel was not added to the precursor dispersion liquid, and other components and amounts were the same as in example 1.
Application example 1
A secondary battery comprising a porous buffer material coated on a surface of a electrode core of the secondary battery;
Wherein the porous buffer material is obtained by polymerizing the precursor dispersion provided in example 1;
the preparation method of the positive electrode plate comprises the following steps: dispersing 98 wt% of positive electrode active substance Li (Ni 0.8Co0.1Mn0.1)O2, 1 wt% of conductive agent carbon black and 1 wt% of binder polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone (NMP) to prepare positive electrode slurry, coating the positive electrode slurry on a current collector aluminum foil and drying, and carrying out rolling, slitting and punching on the dried positive electrode sheet, and then carrying out vacuum high-temperature drying to obtain the positive electrode sheet;
The preparation method of the negative electrode plate comprises the following steps: dispersing 98 wt% of active substance graphite, 0.8% wt% of conductive agent carbon black and 1.2% wt% of binder sodium carboxymethyl cellulose (CMC) in deionized water to prepare negative electrode slurry, coating the negative electrode slurry on copper foil on a current collector, drying, rolling, slitting and punching the dried negative electrode sheet, and then drying at high temperature in vacuum to obtain the negative electrode sheet;
The membrane is a common commercial PE membrane;
The battery shell is made of aluminum alloy;
the electrolyte comprises 30% of ethylene carbonate, 40% of diethyl carbonate, 18% of lithium hexafluorophosphate, 10% of fluoroethylene carbonate and 2% of ethylene sulfate;
the preparation method of the secondary battery provided by the application example comprises the following steps:
(1) Laminating the positive pole piece, the diaphragm and the negative pole piece to obtain a pole core;
(2) Filling the pole core obtained in the step (1) into a battery shell, and packaging to obtain a battery core;
(3) Injecting electrolyte into the battery cell obtained in the step (2) according to the injection amount of 1.8 g/Ah, aging for 20 h at 30 ℃ for the first time, performing negative pressure formation under the vacuum degree of-85 kPa, injecting the precursor solution in the embodiment 1 into the battery cell according to the injection amount of 0.2 g/Ah, aging for 20 h at 25 ℃, overturning for 90 ℃ every 10 min by using a machine, and finally standing for polymerization for 48 h at 50 ℃ for capacity division and coating to obtain the secondary battery.
Application examples 2 to 3
A secondary battery differing from application example 1 only in that the precursor dispersions obtained in examples 2 to 3 were used in place of the precursor dispersion provided in example 1, respectively, and other matters, amounts and preparation methods were the same as those of application example 1.
Application example 4
A secondary battery comprising a porous buffer material coated on a surface of a electrode core of the secondary battery;
wherein the porous buffer material is obtained by polymerizing the precursor dispersion provided in example 4;
the preparation method of the positive electrode plate comprises the following steps: dispersing 98 wt% of positive electrode active material O3-Na (Ni 1/3Fe1/3Mn1/3)O2, 1 wt% of conductive agent carbon black and 1 wt% of binder polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone (NMP) to prepare positive electrode slurry, coating the positive electrode slurry on a current collector aluminum foil, drying, rolling, slitting and punching the dried positive electrode sheet, and then drying at a high temperature in vacuum to obtain the positive electrode sheet;
The preparation method of the negative electrode plate comprises the following steps: dispersing 98 wt% of active substance graphite, 0.8% wt% of conductive agent carbon black and 1.2% wt% of binder sodium carboxymethyl cellulose (CMC) in deionized water to prepare negative electrode slurry, coating the negative electrode slurry on a current collector aluminum foil, drying, rolling, slitting and punching the dried negative electrode sheet, and then drying at a high temperature in vacuum to obtain the negative electrode sheet;
The membrane is a common commercial PE membrane;
The battery shell is made of aluminum alloy;
The electrolyte comprises 30% of ethylene carbonate, 40% of diethyl carbonate, 18% of sodium hexafluorophosphate, 10% of fluoroethylene carbonate and 2% of ethylene sulfate;
the preparation method of the secondary battery provided by the application example comprises the following steps:
(1) Laminating the positive pole piece, the diaphragm and the negative pole piece to obtain a pole core;
(2) Filling the pole core obtained in the step (1) into a battery shell, and packaging to obtain a battery core;
(3) Injecting electrolyte into the battery cell obtained in the step (2) according to the injection amount of 1.8 g/Ah, aging for 20h at 30 ℃ for the first time, performing negative pressure formation under the vacuum degree of-85 kPa, injecting the precursor dispersion in the embodiment 4 into the battery cell according to the injection amount of 0.2 g/Ah, aging for 20h at 25 ℃, overturning for 90 ℃ every 10 min by using a machine, and finally standing for polymerization for 48 h at 50 ℃ for capacity division and coating to obtain the secondary battery.
Application examples 5 to 10
The precursor dispersions obtained in examples 5 to 10 were used to replace the precursor dispersion provided in example 1, and other materials, amounts and preparation methods were the same as those of application example 1.
Application example 11
A secondary battery differing from application example 1 in that step (3) includes: injecting electrolyte into the battery cell obtained in the step (2) according to the injection amount of 1.8 g/Ah, aging for 20 h at 30 ℃, performing negative pressure formation under the vacuum degree of-85 kPa, injecting the precursor dispersion in the embodiment 1 into the battery cell according to the injection amount of 0.2 g/Ah, aging for 20 h at 25 ℃, overturning for 90 degrees by using a machine every 10min, and finally standing for polymerization for 48 h at 20 ℃, and performing capacity division and coating to obtain the secondary battery, wherein other steps are the same as application example 1.
Application example 12
A secondary battery differing from application example 1 in that step (3) includes: injecting electrolyte into the battery cell obtained in the step (2) according to the injection amount of 1.8 g/Ah, aging for 20 h at 30 ℃ for the first time, performing negative pressure formation under the vacuum degree of-85 kPa, injecting the precursor dispersion in the embodiment 1 into the battery cell according to the injection amount of 0.2 g/Ah, aging for 20 h at 25 ℃, overturning for 90 ℃ every 10 min of the battery cell by using a machine, and finally standing for polymerization for 10 h at 70 ℃ for capacity division and coating to obtain the secondary battery, wherein other steps are the same as application example 1.
Application example 13
A secondary battery differing from application example 1 in that the injection amount of the electrolyte in step (3) was 1.7 g/Ah, the injection amount of the precursor dispersion in example 1 was 0.3 g/Ah, and other substances, amounts and production methods were the same as those of application example 1.
Application example 14
A secondary battery differing from application example 1 in that the injection amount of the electrolyte in step (3) was 1.9 g/Ah, the injection amount of the precursor dispersion in example 1 was 0.1 g/Ah, and other substances, amounts and production methods were the same as those of application example 1.
Application example 15
A secondary battery differing from application example 1 in that the injection amount of the electrolyte in step (3) was 1.6 g/Ah, the injection amount of the precursor dispersion in example 1 was 0.4 g/Ah, and other substances, amounts and production methods were the same as those of application example 1.
Application example 16
A secondary battery differing from application example 1 in that the injection amount of the electrolyte in step (3) was 1.95 g/Ah, the injection amount of the precursor dispersion in example 1 was 0.05 g/Ah, and other substances, amounts and production methods were the same as those of application example 1.
Comparative application examples 1 to 3
A secondary battery was different from application example 1 in that the precursor dispersions obtained in comparative examples 1 to 3 were used in place of the precursor dispersion provided in example 1, respectively, and other substances, amounts and production methods were the same as those of application example 1.
Comparative application example 4
A secondary battery differing from application example 1 in that a porous buffer material is not included;
The preparation method of the secondary battery provided by the comparative application example comprises the following steps:
(1) Laminating the positive electrode plate, the diaphragm and the negative electrode plate in application example 1 to obtain a pole core;
(2) Filling the pole core obtained in the step (1) into a battery shell, and packaging to obtain a battery core;
(3) Injecting the electrolyte in application example 1 into the battery cell obtained in the step (2) according to the liquid injection amount of 1.8 g/Ah, aging for 20h at 30 ℃ for the first time, performing negative pressure formation under the vacuum degree of-85 kPa, and finally performing capacity-dividing and coating to obtain the secondary battery.
Comparative application example 5
A secondary battery differing from application example 4 in that a porous buffer material is not included;
The preparation method of the secondary battery provided by the comparative application example comprises the following steps:
(1) Laminating the positive electrode plate, the diaphragm and the negative electrode plate in application example 4 to obtain a pole core;
(2) Filling the pole core obtained in the step (1) into a battery shell, and packaging to obtain a battery core;
(3) Injecting the electrolyte in application example 4 into the battery cell obtained in the step (2) according to the liquid injection amount of 1.8 g/Ah, aging for 20h at 30 ℃ for the first time, performing negative pressure formation under the vacuum degree of-85 kPa, and finally performing capacity-dividing and coating to obtain the secondary battery.
Performance test:
(1) Safety performance: the test is carried out by adopting a hot box, and the specific test method comprises the following steps: firstly, charging a secondary battery to be tested to 4.2V ℃ with a constant current, and then stopping charging when the constant voltage charging reaches a state that the charging termination current is reduced to 0.05C, so that the secondary battery is fully charged; then the temperature line is stuck to the center of the large surface of the secondary battery, and the front and the back surfaces are respectively placed in a hot box at 80 ℃ to be kept at 3 h; then heating at a speed of 5 ℃/min, and keeping 30 min after heating to 5 ℃ until the secondary battery is out of control or the temperature reaches 200 ℃, and ending the test;
(2) Discharge capacity: charging the secondary battery to be tested to 4.2V under constant current of 0.5C at 25 ℃, then stopping charging when the charging termination current is reduced to 0.05C under constant voltage, and standing for 30 min; discharging to 2.8V at a current of 0.5C to obtain a discharge capacity;
(3) Cycle performance: setting the secondary battery to be tested according to the step of capacity test at 25 ℃ for 500 times, and then calculating the ratio of the discharge capacity before and after the cycle to obtain the capacity retention rate;
(4) Internal resistance: firstly, the secondary battery to be tested is charged to 3.65V, and then the internal resistance of the secondary battery is tested by using a voltage internal resistance meter.
The secondary batteries provided in application examples 1 to 16 and comparative application examples 1 to 5 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
From the data in table 1, it can be seen that: the secondary battery containing the porous buffer material provided by the invention has excellent electrochemical performance and safety performance;
Specifically, the secondary battery provided in application examples 1 to 3 is a lithium ion secondary battery including a porous buffer material, which completely passes a thermal runaway safety performance test at 200 ℃, and the discharge capacity is as high as 51.2 to 51.5 ah, the retention rate of 500 charge-discharge cycle capacity is still as high as 95.8 to 96.2%, the internal resistance is only 1.85 to 1.89 mΩ, the secondary battery provided in application example 4 is a sodium ion secondary battery including a porous buffer material, which also passes a thermal runaway safety performance test at 200 ℃, the discharge capacity is as high as 51.0 ah, the retention rate of 500 charge-discharge cycle capacity is as high as 90.6%, and the internal resistance is only 1.86 m Ω, which indicates that the electrochemical performance and thermal safety of the secondary battery provided in application examples 1 to 4 are excellent;
Compared with the secondary battery provided in application example 1, the thermal safety of the secondary battery provided in application examples 5-10 is reduced, which means that the addition amount of the foaming agent, the getter material and the heat insulation material in the precursor dispersion liquid for forming the porous buffer material is very critical, the addition amount of any component is too low, so that the effect of the prepared porous buffer material on active gas absorption and external high temperature resistance is reduced, and the addition amount of any component is too high, so that the prepared porous buffer material cannot form a uniform porous gel structure and becomes into a broken bean curd shape, and the performance of the secondary battery is further affected;
The thermal safety performance of the secondary battery provided in application example 11 was also lowered as compared with the secondary battery provided in application example 1, because the polymerization reaction temperature was too low after the precursor dispersion was injected, so that the injected precursor dispersion could not be completely formed into a gel-like porous buffer material coated on the surface of the electrode core, and the safety performance of the secondary battery was lowered;
The secondary battery provided in application example 12 had a reduced electrochemical performance compared to the secondary battery provided in application example 1, because the polymerization reaction temperature was too high after the precursor dispersion was injected, which resulted in decomposition of the electrolyte with the additives and lithium salt in the precursor dispersion, and thus a stable SEI film could not be formed and the electrochemical performance of the secondary battery was affected;
compared with the secondary battery provided in application examples 1, 13-14, the thermal safety and electrochemical performance of the secondary battery provided in application example 15 are reduced, because the ratio of the injection amount of the electrolyte to the injection amount of the precursor dispersion liquid is too low, the injection amount ratio of the electrolyte to the precursor dispersion liquid is too low, so that the inside of the battery winding core cannot be completely soaked by the electrolyte, and lithium precipitation is caused, and the electrochemical performance and the safety performance of the secondary battery are further influenced;
Compared with the secondary battery provided in application examples 1, 13-14, the thermal safety of the secondary battery provided in application example 16 is also reduced, because the ratio of the injection amount of the electrolyte to the injection amount of the precursor dispersion is too high, and the ratio of the injection amounts of the electrolyte to the injection amount of the precursor dispersion is too high, so that a porous buffer layer with standard thickness and strength cannot be formed, and the effect of effectively improving the thermal safety of the secondary battery cannot be achieved;
Compared with the secondary battery provided in application example 1, the secondary batteries provided in comparative application examples 1-3 have poorer thermal safety performance, which indicates that the foaming agent, the getter material and the heat insulation material added in the precursor dispersion liquid are all key components for forming the porous buffer material, and the foaming agent, the getter material and the heat insulation material are indispensable;
finally, compared with the secondary battery provided by the application example 1, the thermal safety of the secondary battery provided by the comparison application examples 4-5 can be greatly reduced, and the electrochemical performance is reduced, so that the porous buffer material can not only remarkably improve the thermal safety of the lithium ion battery, but also supplement lithium ions or sodium ions in the electrode core.
The applicant states that the present invention is described by way of the above examples as a porous buffer material, a secondary battery, and a method of preparing the same, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (6)

1. A secondary battery, characterized in that the secondary battery comprises a porous buffer material, wherein the porous buffer material is coated on the surface of a pole core of the secondary battery;
The porous buffer material is obtained by polymerizing a precursor dispersion liquid at 30-60 ℃ for 10-48 hours, wherein the precursor dispersion liquid comprises the following components in parts by weight:
1 part by weight of a polymerized monomer;
0.1-0.5 parts by weight of metal salt;
0.0005-0.4 parts by weight of an initiator;
0.01-0.2 parts by weight of a foaming agent;
0.1-0.5 parts by weight of a getter material;
0.1-0.5 parts by weight of a heat insulating material;
0.1-0.5 parts by weight of a flame retardant additive;
0.1-5 parts by weight of an organic solvent;
The preparation method of the secondary battery comprises the following steps: firstly, injecting electrolyte into an electric core of the secondary battery, then injecting precursor dispersion liquid of the porous buffer material, and obtaining the secondary battery through polymerization reaction;
The mass ratio of the precursor dispersion liquid to the injection amount of the electrolyte is 1 (5-20).
2. The secondary battery according to claim 1, wherein the foaming agent comprises any one or a combination of at least two of N, N' -dinitroso pentamethylene tetramine, ethylene glycol and glycerol;
the getter material comprises a molecular sieve;
The insulating material comprises silica aerogel.
3. The secondary battery according to claim 1, wherein the polymerized monomer is a vinyl-containing monomer including any one or a combination of at least two of n-butyl acrylate, isobutyl acrylate, propyl acrylate, polyethylene glycol methacrylate, polyethylene glycol monomethyl ether methacrylate, 2-methoxyethyl acrylate, ethyl acrylate, hexyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, n-octyl methacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, triethylene glycol diacrylate, glycidyl methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, γ -methacryloxypropyl trimethoxysilane, allyl diethyl phosphate, bis (2-chloroethyl) vinyl phosphate, and allylbiphenyl phosphine oxide.
4. The secondary battery according to claim 1, wherein the metal salt comprises a lithium salt or a sodium salt;
the initiator includes a peroxide initiator and/or an azo compound initiator.
5. The secondary battery according to claim 1, wherein the organic solvent comprises a phosphorus-containing organic solvent and/or a halogen-containing organic solvent;
The flame retardant additive comprises any one or a combination of at least two of hexamethoxy phosphazene, bis (methoxyethoxyethoxy) phosphazene, hexaethoxy phosphazene, 4-methoxy-phenoxy pentafluoro-cyclotriphosphazene, decabromodiphenyl ether, tetrabromobisphenol A and tetrabromobisphenol A bis (2.3-dibromopropyl) ether (octabromoether).
6. The method for manufacturing a secondary battery according to any one of claims 1 to 5, comprising: and firstly injecting electrolyte into the battery core of the secondary battery, then injecting precursor dispersion liquid of the porous buffer material, and obtaining the secondary battery through polymerization reaction.
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