CN114188595A - Solid polymer electrolyte and lithium ion battery comprising same - Google Patents

Solid polymer electrolyte and lithium ion battery comprising same Download PDF

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Publication number
CN114188595A
CN114188595A CN202010969104.9A CN202010969104A CN114188595A CN 114188595 A CN114188595 A CN 114188595A CN 202010969104 A CN202010969104 A CN 202010969104A CN 114188595 A CN114188595 A CN 114188595A
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polymer electrolyte
solid polymer
polyether
formula
comparative example
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唐伟超
李素丽
赵伟
李俊义
徐延铭
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Zhuhai Cosmx Battery Co Ltd
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Priority to CN202010969104.9A priority Critical patent/CN114188595A/en
Priority to PCT/CN2021/116762 priority patent/WO2022057665A1/en
Publication of CN114188595A publication Critical patent/CN114188595A/en
Priority to US18/168,745 priority patent/US20230265223A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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 solid polymer electrolyte and a lithium ion battery comprising the solid polymer electrolyte; the solid polymer electrolyte comprises a polymer and lithium salt, wherein the polymer contains acrylate, polyether boric acid ester, polyether aluminate or polyether phosphate structure, and the polymer has a comb structure; compared with polyethylene oxide (PEO) polymer electrolyte, the solid polymer electrolyte has higher conductivity, higher lithium ion conductivity, better mechanical property, higher battery cycle performance and higher electrochemical window, and has certain application potential.

Description

Solid polymer electrolyte and lithium ion battery comprising same
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a solid polymer electrolyte and a lithium ion battery comprising the same.
Background
Because the lithium ion battery has the advantages of high energy density, long cycle life, small self-discharge rate, environmental protection and the like, the lithium ion battery is widely applied to consumer electronics products such as energy storage fields, power automobiles, notebook computers, mobile phones, cameras and the like. However, the main limitations currently limiting the development of lithium ion batteries are energy density and safety. The solid-state battery has good application potential as the next generation lithium ion battery which is closest to practical application.
The solid-state battery mainly comprises a solid-state anode, a solid-state electrolyte and a solid-state cathode, wherein the solid-state electrolyte is used for separating the solid-state anode and the solid-state cathode and conducting lithium ions and is always a core material of the solid-state battery. Solid electrolytes are currently mainly classified into polymer electrolytes, oxide electrolytes, sulfide electrolytes, and hydride electrolytes. The oxide electrolyte has the problems of poor solid-solid interface, fragile material, high processing difficulty and the like; sulfide electrolyte has the problems of poor solid-solid interface, high cost, poor material stability and the like; the hydride electrolyte has the problems of poor compatibility with a high-energy-density positive electrode, insufficient maturity of materials and the like. The polymer electrolyte has the advantages of good flexibility, low processing difficulty, low density and the like, and has good application potential in the field of power batteries.
However, the conventional polymer electrolyte is mainly represented by polyethylene oxide (PEO), and the polyethylene oxide material has problems of certain crystallinity, intolerance to high voltage, low conductivity, and the like. This severely limited the development of solid electrolytes.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a solid polymer electrolyte and a lithium ion battery comprising the solid polymer electrolyte; the solid polymer electrolyte comprises a polymer and lithium salt, wherein the polymer contains acrylate, polyether boric acid ester, polyether aluminate or polyether phosphate structure, and the polymer has a comb structure; compared with polyethylene oxide (PEO) polymer electrolyte, the solid polymer electrolyte has higher conductivity, higher lithium ion conductivity, better mechanical property, higher battery cycle performance and higher electrochemical window, and has certain application potential.
The purpose of the invention is realized by the following technical scheme:
a solid polymer electrolyte comprising a polymer and a lithium salt, the polymer comprising a repeating unit represented by the following formula 1:
Figure BDA0002683417270000021
in the formula 1, R1Is selected from H or C1-6An alkyl group; r2Is a linking group; r3Is a capping group; m is selected from a borate segment, an aluminate segment, or a phosphate segment; denotes the connection end.
According to the invention, R1Is selected from H or C1-3An alkyl group; such as R1Selected from H or methyl.
According to the invention, R3Selected from H, OH or COOH.
According to the invention, the polymer has a comb-like structure.
According to the invention, the borate segment has a structural unit represented by formula 2 or formula 3:
Figure BDA0002683417270000022
Figure BDA0002683417270000031
in formula 2 and formula 3, a represents the link end, and n is the degree of polymerization.
According to the invention, the aluminate chain segment has a structural unit represented by formula 4:
Figure BDA0002683417270000032
in formula 4, denotes a connection end, and m is a polymerization degree.
According to the invention, the phosphate segment has a structural unit represented by formula 5:
Figure BDA0002683417270000033
in formula 5, represents and R3Denotes a connection with R2Q is the degree of polymerization.
According to the invention, the number average molecular weight of M is 200-10000.
According to the invention, the polymer is selected from at least one of poly (polyether borate acrylate), poly (polyether aluminate acrylate), poly (polyether phosphate acrylate), poly (polyether borate methacrylate), poly (ether aluminate methacrylate), poly (ether phosphate methacrylate).
According to the invention, the number average molecular weight of the polymer is 4000 to 300000.
According to the invention, the monomers for preparing the polymer are selected from the compounds represented by the following formula 6:
Figure BDA0002683417270000041
in the formula 6, R1、R2、R3M is as defined above.
According to the invention, the compound shown in the formula 6 is at least one selected from polyether borate acrylate, polyether aluminate acrylate, polyether phosphate acrylate, polyether borate methacrylate, polyether aluminate methacrylate and polyether phosphate methacrylate.
According to the present invention, the solid polymer electrolyte further comprises an auxiliary agent.
According to the invention, the solid polymer electrolyte comprises the following components in percentage by mass: 60-90 wt% of polymer, 10-30 wt% of lithium salt and 0-10 wt% of assistant.
According to the present invention, the assistant includes at least one of an oxide electrolyte, a nano filler, and an organic assistant.
Wherein the oxide electrolyte is selected from at least one of lithium phosphate, lithium titanate, lithium titanium phosphate, lithium aluminum titanium phosphate, lithium lanthanum titanate, lithium lanthanum tantalate, lithium aluminum germanium phosphate, lithium aluminosilicate, lithium silicophosphate, lithium lanthanum titanate and boron trioxide doped lithium phosphate.
Wherein the nano filler is selected from at least one of aluminum oxide, magnesium oxide, boehmite, barium sulfate, barium titanate, zinc oxide, calcium oxide, silicon dioxide, silicon carbide and nickel oxide.
Wherein the organic auxiliary agent is at least one selected from methoxy polyethylene glycol borate (B-PEG), methoxy polyethylene glycol aluminate (Al-PEG), succinonitrile, ethylene carbonate, vinylene carbonate, fluoroethylene carbonate and tetraethylene glycol dimethyl ether.
According to the present invention, the solid polymer electrolyte is preferably a solid polymer electrolyte membrane.
According to the invention, the thickness of the solid polymer electrolyte membrane is 10-150 μm.
A lithium ion battery comprising the solid polymer electrolyte.
According to the present invention, the solid polymer electrolyte membrane of the lithium ion battery includes the above-described solid polymer electrolyte.
Has the advantages that:
the invention provides a solid polymer electrolyte and a lithium ion battery comprising the solid polymer electrolyte; the solid polymer electrolyte has higher lithium ion conductivity. Compared with the conventional polymer electrolyte (such as PEO polymer electrolyte), the solid polymer of the invention has a lower crystallization degree due to the branched structure, and lithium ions have higher lithium ion conductivity in an amorphous region of the solid polymer electrolyte; meanwhile, the branched chain of the solid polymer is polyether boric acid ester, polyether aluminate or polyether phosphate, and the branched chain structure can also effectively promote the dissociation of lithium salt in the solid polymer electrolyte, so that the conductivity of lithium ions is further improved;
the lithium ion battery prepared by using the solid polymer electrolyte has better mechanical property and cycle performance. The solid polymer is a polymer with a comb-shaped polyether structure, the polymer with the comb-shaped polyether structure can improve the mechanical property of the solid polymer electrolyte, and compared with the conventional polymer electrolyte (such as PEO polymer electrolyte), the solid polymer electrolyte provided by the invention has better mechanical property under the same thickness, and can effectively improve the cycle performance of a battery;
the solid polymer electrolyte has a higher electrochemical window and can be matched with a high-voltage system. The main chain of the solid polymer electrolyte adopts acrylic ester as a reactive group, the branched chain is polyether boric acid ester, polyether aluminate or polyether phosphate and the like, the addition of the polyether boric acid ester, the polyether aluminate or the polyether phosphate can effectively improve the electrochemical window of the solid polymer electrolyte, and the solid polymer electrolyte can be matched with a high-voltage system material to prepare the lithium ion battery with higher energy density.
Detailed Description
< solid Polymer electrolyte >
As described above, the present invention provides a solid polymer electrolyte comprising a polymer and a lithium salt, the polymer comprising a repeating unit represented by the following formula 1:
Figure BDA0002683417270000061
in the formula 1, R1Is selected from H or C1-6An alkyl group; r2Is a linking group; r3Is a capping group; m is selected from a borate segment, an aluminate segment, or a phosphate segment; denotes the connection end.
In one embodiment of the invention, the polymer has a comb-like structure.
In one embodiment of the invention, R1Is selected from H or C1-3An alkyl group; such as R1Selected from H or methyl.
In one embodiment of the invention, R3Selected from H, OH or COOH.
In one embodiment of the invention, R2Is composed of
Figure BDA0002683417270000062
Hydroxy in (A) and
Figure BDA0002683417270000063
r in (1)3' A linking group formed after the reaction, substantially, R2Is R3' wherein, R3' and R3Identical or different, independently of one another, from H, OH, COOH.
In one embodiment of the present invention, the borate segment has a structural unit represented by formula 2 or formula 3:
Figure BDA0002683417270000064
Figure BDA0002683417270000071
in formula 2 and formula 3, a represents the link end, and n is the degree of polymerization.
In one embodiment of the present invention, the aluminate segment has a structural unit represented by formula 4:
Figure BDA0002683417270000072
in formula 4, denotes a connection end, and m is a polymerization degree.
In one embodiment of the present invention, the phosphate segment has a structural unit represented by formula 5:
Figure BDA0002683417270000073
in formula 5, represents and R3Is connected toEnd, represents and R2Q is the degree of polymerization.
In one embodiment of the present invention, M has a number average molecular weight of 200 to 10000.
In one embodiment of the invention, the polymer is selected from at least one of poly (polyether borate acrylate), poly (polyether aluminate acrylate), poly (polyether phosphate acrylate), poly (polyether borate methacrylate), poly (ether aluminate methacrylate), poly (ether phosphate methacrylate).
In one embodiment of the present invention, the number average molecular weight of the polymer is 4000 to 300000.
In one embodiment of the present invention, the monomer for preparing the polymer is selected from the group consisting of compounds represented by the following formula 6:
Figure BDA0002683417270000081
in the formula 6, R1、R2、R3M is as defined above.
In one embodiment of the present invention, the compound represented by formula 6 is at least one selected from the group consisting of polyether borate acrylate, polyether aluminate acrylate, polyether phosphate acrylate, polyether borate methacrylate, polyether aluminate methacrylate, and polyether phosphate methacrylate.
In one aspect of the present invention, the solid polymer electrolyte further includes an auxiliary agent.
In one embodiment of the present invention, the solid polymer electrolyte comprises the following components by mass: 60-90 wt% of polymer, 10-30 wt% of lithium salt and 0-10 wt% of assistant.
Illustratively, the polymer is present in an amount of 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 89.9 wt%, or 90 wt% by mass.
Illustratively, the lithium salt is present in an amount of 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, or 30 wt% by mass.
Illustratively, the mass percentage of the auxiliary agent is 0 wt%, 0.1 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%.
In one embodiment of the present invention, the lithium salt is selected from lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Lithium hexafluoroarsenate (LiAsF)6) Lithium tetrafluoroborate (LiBF)4) Lithium bis (oxalato) borate (LiBOB), lithium bis (oxalato) difluoroborate (LiDFOB), lithium bis (difluorosulfonimide) (LiFSI), lithium bis (trifluoromethylsulfonimide) (LiTFSI), lithium (trifluoromethylsulfonate) (LiCF)3SO3) Bis (malonic) boronic acid (LiBMB), lithium oxalatoborate malonate (LiMOB), lithium hexafluoroantimonate (LiSbF)6) Lithium difluorophosphate (LiPF)2O2) Lithium 4, 5-dicyano-2-trifluoromethylimidazole (LiDTI), lithium bis (trifluoromethylsulfonyl) imide (LiN (SO)2CF3)2)、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO2F)2One or any combination of (a).
In one aspect of the present invention, the assistant includes at least one of an oxide electrolyte, a nanofiller, and an organic assistant.
Wherein the oxide electrolyte is selected from at least one of lithium phosphate, lithium titanate, lithium titanium phosphate, lithium aluminum titanium phosphate, lithium lanthanum titanate, lithium lanthanum tantalate, lithium aluminum germanium phosphate, lithium aluminosilicate, lithium silicophosphate, lithium lanthanum titanate and boron trioxide doped lithium phosphate.
Wherein the nano filler is selected from at least one of aluminum oxide, magnesium oxide, boehmite, barium sulfate, barium titanate, zinc oxide, calcium oxide, silicon dioxide, silicon carbide and nickel oxide.
Wherein the organic auxiliary agent is at least one selected from methoxy polyethylene glycol borate (B-PEG), methoxy polyethylene glycol aluminate (Al-PEG), succinonitrile, ethylene carbonate, vinylene carbonate, fluoroethylene carbonate and tetraethylene glycol dimethyl ether.
In one aspect of the present invention, the solid polymer electrolyte is preferably a solid polymer electrolyte membrane.
In one aspect of the present invention, the thickness of the solid polymer electrolyte membrane is 10 to 150 μm.
< preparation of solid Polymer electrolyte >
The invention also provides a preparation method of the solid polymer electrolyte, which comprises the following steps:
(1) uniformly mixing a first solvent, a polymer monomer shown as a formula 6 and an initiator, and heating to perform a polymerization reaction to prepare a polymer;
(2) and (2) mixing the polymer obtained in the step (1), a lithium salt, an optional auxiliary agent and a second solvent, coating the mixture on the surface of a substrate, and drying the mixture in an inert atmosphere to obtain the solid polymer electrolyte.
In one scheme of the invention, in the step (1), the mixture is stirred for 60-400 min at a rotating speed of 200-2000 r/min; the mixing is carried out under an inert atmosphere.
In one embodiment of the present invention, in the step (1), the initiator is added in an amount of 0.01 to 0.5 wt% based on the total mass of the polymer monomers represented by the formula 6. The amount of the first solvent added is 1 to 10 times of the total mass of the polymer monomers represented by the formula 6. Illustratively, the first solvent and the polymer monomer represented by the formula 6 are added in an amount of 60 to 100g of the polymer monomer represented by the formula 6 and 100 to 600g of the first solvent.
In one embodiment of the invention, in the step (1), the temperature of the polymerization reaction is 50 ℃ to 90 ℃, and the time of the polymerization reaction is 2 to 60 hours.
In one embodiment of the present invention, in step (1), the initiator may be one or more selected from azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert-butyl peroxide, ethyl 4- (N, N-dimethylamino) benzoate, methyl o-benzoylbenzoate, etc.
In one scheme of the invention, in the step (2), the mixture is stirred for 2-15 hours at a rotating speed of 200-2000 r/min; the mixing is carried out under an inert atmosphere.
In one scheme of the invention, in the step (2), the drying temperature is 60-100 ℃, and the drying time is 24-80 h.
In one embodiment of the present invention, in step (2), the drying process may remove excess solvent to prepare the solid polymer electrolyte.
In one embodiment of the invention, in the step (2), the mass ratio of the polymer, the lithium salt and the optional auxiliary agent in the step (1) is 60-90: 10-30: 0 to 10.
In one embodiment of the present invention, in the step (2), the polymer and the second solvent in the step (1) are added in an amount of 60 to 90: 100 to 800.
In one embodiment of the present invention, in the step (1), the first solvent is at least one selected from N-methylpyrrolidone, acetonitrile, hydrofluoroether, acetone, tetrahydrofuran, dichloromethane, pyridine, etc., xylene, and toluene.
In one embodiment of the present invention, in the step (2), the second solvent is at least one selected from N-methylpyrrolidone, acetonitrile, hydrofluoroether, acetone, tetrahydrofuran, dichloromethane, pyridine, etc., xylene, and toluene.
Illustratively, the method for preparing the solid polymer electrolyte comprises the following steps:
s1: stirring 60-100 g of functional monomer and 100-600 g of solvent for 60-400 min at a rotating speed of 200-2000 r/min in an inert gas atmosphere, then adding 0.01-0.2 g of initiator, then reacting for 2-60 h at 50-90 ℃, and obtaining a polymer A system after purification treatment;
s2: adding 60-90 g of polymer A system, 10-30 g of lithium salt and 0-10 g of auxiliary agent into 100-800 g of solvent, stirring at a rotating speed of 200-2000 r/min in an inert gas atmosphere for 2-15 h, uniformly coating the mixed solution on a mold with a smooth surface, introducing inert gas into a vacuum drying oven, standing for 10-64 h in the inert gas atmosphere, removing the redundant solvent, and drying in the vacuum drying oven at 60-100 ℃ for 24-80 h to obtain the solid polymer electrolyte.
< lithium ion Battery >
As mentioned above, the present invention also provides a lithium ion battery comprising the above solid polymer electrolyte.
In one aspect of the present invention, the lithium ion battery further includes a positive electrode and a negative electrode.
In one aspect of the invention, the lithium ion battery includes a solid polymer electrolyte membrane.
In one aspect of the present invention, the solid polymer electrolyte membrane of the lithium ion battery includes the above-described solid polymer electrolyte.
In one aspect of the present invention, the solid polymer electrolyte membrane is disposed between a positive electrode and a negative electrode.
In one embodiment of the present invention, a solid lithium ion battery cell is prepared by laminating a positive electrode plate, the solid polymer electrolyte (preferably a solid polymer electrolyte membrane), and a negative electrode plate, and is welded and packaged to obtain a lithium ion battery.
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention. The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
"W" in the molecular weight of the polymer or polymer monomer used in the following examples represents ten thousand, such as 4W, that is, 4 ten thousand.
The polyether acrylates and polyether methacrylates used in the following examples have the formula 7:
Figure BDA0002683417270000121
wherein, when the polyether acrylate is used, R1Is H, R2Is absent, R3Is H.
Wherein, if the polyether methacrylate is adopted, R is1Is CH3、R2Is absent, R3Is H.
The polyether borate used in the following examples has the formula 8:
Figure BDA0002683417270000122
the structural formula of the polyether aluminate used in the following examples is shown in formula 9:
Figure BDA0002683417270000123
the structural formula of the polyether phosphate used in the following examples is shown in formula 10:
Figure BDA0002683417270000124
example 1
1) Preparation of solid electrolyte membrane:
s1: keeping 75g of functional monomer polyether borate acrylate and 300g of first solvent in an inert gas atmosphere, stirring at the rotating speed of 800r/min for 200min, then adding 0.05g of initiator azobisisobutyronitrile, reacting at 60 ℃ for 4h, and purifying to obtain a polymer;
s2: adding 30g of the prepared polymer poly (polyether borate acrylate), 5g of lithium salt and 2g of auxiliary agent into 300g of second solvent, stirring at the rotating speed of 1000r/min under the atmosphere of dry inert gas for 4h, uniformly coating the mixed solution on a mold with a smooth surface, introducing inert gas into a vacuum drying box, standing for 24h in the atmosphere of inert gas to remove redundant solvent, and drying at 80 ℃ for 30h in the vacuum drying box to obtain a solid polymer electrolyte membrane;
2) preparing a positive pole piece:
uniformly mixing 80g of positive active material, 5g of conductive agent, 12g of polymer electrolyte, 2g of lithium salt, 1g of binder and 200g of solvent, coating the mixture on the surface of an aluminum foil current collector, and drying, rolling and slitting the mixture to obtain a positive pole piece;
3) preparing a negative pole piece:
dissolving 2g of silicon monoxide, 3g of lithium metal powder, 4g of conductive carbon black serving as a conductive agent and 0.5g of adhesive oil system acrylate in 100g of p-xylene, uniformly mixing, coating on the surface of a copper foil of a negative current collector, drying (the temperature is 100 ℃, the time is 20h, and the atmosphere of argon gas), rolling and die-cutting to obtain a negative pole piece;
4) preparation of lithium ion battery
And preparing a solid lithium ion battery cell by laminating the obtained positive pole piece, the obtained solid electrolyte membrane and the obtained negative pole piece, and welding and packaging to obtain the lithium ion battery.
Comparative example 1.1
The specific process is as in example 1, with the main differences: in comparative example 1.1, an equal mass of polyether borate was used instead of the polyether borate acrylate of example 1, otherwise the conditions were identical to those of example 1.
Comparative example 1.2
The specific process is as in example 1, with the main differences: in comparative example 1.2, instead of the polyether borate acrylate of example 1, a mixture of polyether borate and polyacrylate in equal mass to the polyether borate acrylate monomer was used, wherein the mass ratio of polyether borate to polyacrylate was the molecular weight ratio of polyether borate to acrylate in the polyether borate acrylate monomer, and the other conditions were identical to those of example 1.
Comparative example 1.3
The specific process is as in example 1, with the main differences: in comparative example 1.3, a polyether acrylate of equal mass to the polyether borate acrylate monomer was used instead of the polyether borate acrylate of example 1, otherwise the conditions were identical to those of example 1.
Other examples and other comparative examples
The specific process is as in example 1 with the main differences: the preparation process conditions, the adding amount of each component and the types of materials of each component of the solid polymer electrolyte are shown in the table 1 and the table 2 in detail. Among them, in comparative examples in which two polymers were added in table 2, the amounts of the two polymers added were ratios of the polymer segments and the molecular weights of the poly (meth) acrylate in the polymerized monomers added in the corresponding examples, specifically, see the description in comparative examples 1 to 2 described above.
TABLE 1 preparation component contents of solid polymer electrolytes of examples and comparative examples
Serial number First solvent/g Functional monomer/g Initiator/g Polymer/g Lithium salt/g Adjuvant/g Second solvent/g
Example 1 300 75 0.05 30 5 2 200
Comparative example 1.1 300 75 0.05 30 5 2 200
Comparative example 1.2 300 75 0.05 30 5 2 200
Comparative example 1.3 300 75 0.05 30 5 2 200
Example 2 500 95 0.09 80 20 5 700
Comparative example 2.1 500 95 0.09 80 20 5 700
Comparative example 2.2 500 95 0.09 80 20 5 700
Comparative example 2.3 500 95 0.09 80 20 5 700
Example 3 550 90 0.15 75 25 8 600
Comparative example 3.1 550 90 0.15 75 25 8 600
Comparative example 3.2 550 90 0.15 75 25 8 600
Comparative example 3.3 550 90 0.15 75 25 8 600
Example 4 100 60 0.01 90 32 10 500
Comparative example 4.1 100 60 0.01 90 32 10 500
Comparative example 4.2 100 60 0.01 90 32 10 500
Comparative example 4.3 100 60 0.01 90 32 10 500
Example 5 600 100 0.2 50 18 0 300
Comparative example 5.1 600 100 0.2 50 18 0 300
Comparative example 5.2 600 100 0.2 50 18 0 300
Comparative example 5.3 600 100 0.2 50 18 0 300
Example 6 300 80 0.06 100 40 1 800
Comparative example 6.1 300 80 0.06 100 40 1 800
Comparative example 6.2 300 80 0.06 100 40 1 800
Comparative example 6.3 300 80 0.06 100 40 1 800
TABLE 2 preparation component composition of solid Polymer electrolytes of examples and comparative examples
Figure BDA0002683417270000151
And (3) performance testing:
solid polymer electrolyte conductivity test method: and cutting the solid polymer electrolyte film, assembling the cut solid polymer electrolyte film and the processed stainless steel gasket into a stainless steel/solid electrolyte/stainless steel button cell, and testing the diameter of the stainless steel gasket and the thickness of the solid polymer electrolyte. The battery is tested and calculated by adopting 100 KHz-0.1 mHz frequency under the condition of 60 ℃ by adopting a Metrohm Switzerland PGSTAT302N chemical workstation.
Electrochemical window test method: a button cell assembled by stainless steel/solid electrolyte/lithium metal is tested at 2V-5V by adopting a Metrohm Switzerland PGSTAT302N chemical workstation at 25 ℃.
Table 3 conductivity and electrochemical window test results of solid polymer electrolytes of examples and comparative examples
Serial number Conductivity at 25 ℃ (mS/cm) Electrochemical window (V)
Example 1 1.65 4.40
Comparative example 1.1 2.54 4.30
Comparative example 1.2 0.83 4.35
Comparative example 1.3 1.59 4.15
Example 2 1.89 4.35
Comparative example 2.1 2.67 4.25
Comparative example 2.2 0.92 4.30
Comparative example 2.3 1.75 4.10
Example 3 2.34 4.30
Comparative example 3.1 4.52 4.20
Comparative example 3.2 1.43 4.25
Comparative example 3.3 2.27 4.10
Example 4 2.83 4.45
Comparative example 4.1 3.21 4.30
Comparative example 4.2 1.03 4.40
Comparative example 4.3 2.31 4.10
Example 5 2.12 4.35
Comparative example 5.1 2.83 4.25
Comparative example 5.2 1.27 4.20
Comparative example 5.3 2.05 4.05
Example 6 2.21 4.35
Comparative example 6.1 3.32 4.30
Comparative example 6.2 1.62 4.35
Comparative example 6.3 2.04 4.15
The conductivity and electrochemical window test results of the solid polymer electrolyte show that: the polymer electrolyte prepared by polymerizing the polymer monomer with the specific structure in the embodiment of the invention has higher conductivity; in the comparative examples, polyether ester (polyether aluminate, polyether borate or polyether phosphate) + polyacrylate and polyether acrylate are used, and in the comparative example 1.1, because polyether ester (polyether aluminate, polyether borate or polyether phosphate) with the same structure is used, the electrochemical window is close and the conductivity is higher in the data test; in the comparative example 1.2, polyether ester (polyether aluminate, polyether borate or polyether phosphate) and polyacrylate are blended, and the polyacrylate does not have lithium-conducting performance, so that the conductivity is low; comparative example 1.3 uses a polyether acrylate polymer, where the conductivity is close to that of the example, but the electrochemical window is lower.
TABLE 4 Battery cycling Performance of examples and comparative examples
Serial number Cycle performance 0.3C/0.3C
Example 1 1020 cycles (80%)
Comparative example 1.1 10 times cycle (short circuit of battery)
Comparative example 1.2 3 times cycle (short circuit of battery)
Comparative example 1.3 650 cycles (80%)
Example 2 3030 cycles (80%)
Comparative example 2.1 5 times cycle (short circuit of battery)
Comparative example 2.2 12 times cycle (short circuit of battery)
Comparative example 2.3 2700 cycles (80%)
Example 3 520 cycles (80%)
Comparative example 3.1 7 times cycle (short circuit of battery)
Comparative example 3.2 15 times cycle (short circuit of battery)
Comparative example 3.3 312 cycles (80%)
Example 4 1810 cycles (80%)
Comparative example 4.1 6 times cycle (short circuit of battery)
Comparative example 4.2 14 cycles (short circuit of battery)
Comparative example 4.4 1205 cycles (80%)
Example 5 2579 cycles (80%)
Comparative example 5.1 7 times cycle (short circuit of battery)
Comparative example 5.2 19 times cycle (short circuit of battery)
Comparative example 5.3 1610 cycles (80%)
Example 6 1536 cycles (80%)
Comparative example 6.1 2 times cycle (short circuit of battery)
Comparative example 6.2 17 times cycle (short circuit of battery)
Comparative example 6.3 945 cycles (80%)
Example 7 1852 circulation (80%)
Comparative example 7.1 5 times cycle (short circuit of battery)
Comparative example 7.2 14 cycles (short circuit of battery)
Comparative example 7.3 1062 cycles (80%)
The battery cycle performance test method comprises the following steps: the lithium ion battery is subjected to a charge-discharge cycle test on a blue battery charge-discharge test cabinet under the test conditions of 60 ℃ and 0.3C/0.3C charge-discharge, and the cycle number when the battery capacity retention rate is reduced to 80% is inspected.
The cycle performance test results of the lithium ion batteries of the examples and comparative examples show that: the lithium ion battery prepared by the embodiment of the invention has good cycle performance; taking one group of comparative examples as an example, the small molecules of the non-polymerizable material exist in the battery in the comparative example 1.1, and the small molecules are easy to cause short circuit of the battery in a high-voltage system; in comparative example 1.2, small molecules which are not polymerizable are present in the cell, but the polymer small molecule content is slightly low, so the cycle performance is higher than that of comparative example 1.1, but short circuit is easy; comparative example 1.3 compared with example 1, the main difference is that polyether acrylate has a lower electrochemical window compared with polyether borate acrylate, polyether aluminate acrylate and polyether phosphate acrylate, so that the oxidative decomposition is too fast in the circulation process, and the circulation performance is affected.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A solid polymer electrolyte comprising a polymer and a lithium salt, the polymer comprising a repeating unit represented by the following formula 1:
Figure FDA0002683417260000011
in the formula 1, R1Is selected from H or C1-6An alkyl group; r2Is a linking group; r3Is a capping group; m is selected from a borate segment, an aluminate segment, or a phosphate segment; denotes the connection end.
2. The solid polymer electrolyte of claim 1 wherein R1Is selected from H or C1-3An alkyl group; such as R1Selected from H or methyl; and/or the presence of a gas in the gas,
R3selected from H, OH or COOH.
3. The solid polymer electrolyte of claim 1 or 2, wherein the borate segment has a structural unit represented by formula 2 or formula 3:
Figure FDA0002683417260000012
in formula 2 and formula 3, a represents the link end, and n is the degree of polymerization.
4. The solid polymer electrolyte of claim 1 or 2, wherein the aluminate segment has a structural unit represented by formula 4:
Figure FDA0002683417260000021
in formula 4, denotes a connection end, and m is a polymerization degree.
5. The solid polymer electrolyte of claim 1 or 2, wherein the phosphate segment has a structural unit represented by formula 5:
Figure FDA0002683417260000022
in formula 5, represents and R3Denotes a connection with R2Q is the degree of polymerization.
6. The solid polymer electrolyte of any of claims 1-5, wherein M has a number average molecular weight of 200 to 10000.
7. The solid polymer electrolyte of any of claims 1-6, wherein the polymer is selected from at least one of poly (polyether borate acrylate), poly (polyether aluminate acrylate), poly (polyether phosphate acrylate), poly (polyether borate methacrylate), poly (ether aluminate methacrylate), poly (ether phosphate methacrylate); and/or the presence of a gas in the gas,
the number average molecular weight of the polymer is 4000-300000.
8. The solid polymer electrolyte of any of claims 1-7, further comprising an additive, wherein the solid polymer electrolyte comprises the following components in percentage by mass: 60-90 wt% of polymer, 10-30 wt% of lithium salt and 0-10 wt% of assistant.
9. The solid polymer electrolyte of any of claims 1-8, wherein the solid polymer electrolyte is preferably a solid polymer electrolyte membrane; and/or the presence of a gas in the gas,
the thickness of the solid polymer electrolyte membrane is 10-150 mu m.
10. A lithium-ion battery comprising the solid polymer electrolyte of any one of claims 1-9.
CN202010969104.9A 2020-09-15 2020-09-15 Solid polymer electrolyte and lithium ion battery comprising same Pending CN114188595A (en)

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