CN116365054B - Aqueous solid electrolyte slurry, solid electrolyte membrane and secondary battery - Google Patents
Aqueous solid electrolyte slurry, solid electrolyte membrane and secondary battery Download PDFInfo
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
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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
- 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
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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Abstract
The invention relates to the technical field of secondary batteries, in particular to an aqueous solid electrolyte slurry, a solid electrolyte diaphragm and a secondary battery. The aqueous solid electrolyte slurry includes: solid electrolyte, water-based adhesive thickener, phthalocyanine material, silicate material, wetting agent and water; the solid electrolyte, the water-based adhesive thickener, the phthalocyanine salt material, the silicate material and the wetting agent are in a mass ratio of 90-110: 3-10: 0.01-0.05: 0.01 to 0.02:0.05 to 0.15. Through the composite use of the phthalocyanine salt material and the silicate material, the structural stability of the solid electrolyte material in the aqueous solution can be protected from the formula level by matching with other components, so that the structural stability of the solid electrolyte in the slurry is ensured, the ion conductivity performance loss of the solid electrolyte is reduced, and the expected effect of the solid electrolyte with high ion conductivity function is ensured to be exerted.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to an aqueous solid electrolyte slurry, a solid electrolyte diaphragm and a secondary battery.
Background
The existing lithium battery separator coating mainly uses materials such as alumina, boehmite, magnesium hydroxide and the like as main materials to manufacture coating slurry, the slurry is coated on a separator and dried to form a ceramic coating mainly made of the materials such as alumina, boehmite, magnesium hydroxide and the like, so that the effects of improving the heat stability of the separator, the wettability of electrolyte and the like are achieved, the battery performance is improved, and the coating materials do not have ionic conductivity, so that the ionic conductivity of the separator is not improved.
Oxide solid electrolyte material Li 1+x Al x Ti 2-x (PO 4 ) 3 （0<x<2) And Li (lithium) 3y La 2/(3-y) TiO 3 （0<y<0.167 As a novel ceramic coating host material to replace existing alumina, boehmite, magnesium hydroxide, etc. due to its excellent ion conductivity propertiesThe ceramic coating is used as a main material to ensure that the coating of the diaphragm has higher ionic conductivity, thereby optimizing the performance of the lithium battery. However, only the conductivity of the oxide solid electrolyte materials is concerned, but the stability of the oxide solid electrolyte materials is not concerned after the oxide solid electrolyte materials are blended with a solvent and an auxiliary agent in the process of manufacturing coating slurry, so that the problems of ion precipitation and the like of the oxide solid electrolyte materials in the slurry are caused, the ion conductivity performance of the oxide solid electrolyte materials is influenced, and a better effect cannot be achieved.
Patent CN 114464950A discloses a high ionic conductivity type diaphragm, which comprises a base film and a composite ceramic coating layer arranged on the base film, wherein the composite ceramic coating layer comprises conductive ceramic and a polymer coated on the conductive ceramic, the polymer is at least one of polyethylene, polyethylene wax, polyethylene oxide wax, polypropylene wax and linear low density polyethylene, and the composite ceramic coating layer contains at least one of zirconium metal oxide and tantalum metal oxide and also comprises an adhesive layer arranged on the base film and/or the composite ceramic coating layer. However, in the practical production of the technical scheme, the problem of precipitation of lithium ions in the aqueous solution exists in the main material, so that the main material is damaged in structure, the ionic conductivity is abnormal, the slurry stability is abnormal (pH value change, particle agglomeration, slurry gel and the like), the ionic conductivity of the coating is influenced, the coating cannot play an expected role, and meanwhile, the slurry stability period is short, so that the requirement of mass production investment cannot be met.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an aqueous solid electrolyte slurry, a solid electrolyte membrane and a secondary battery, which solve the problem of stability of solid electrolyte (described as conductive ceramic in the background art) in aqueous solution, and the electrochemical performance of the secondary battery prepared from the aqueous solid electrolyte slurry is better.
The invention provides an aqueous solid electrolyte slurry, comprising: solid electrolyte, water-based adhesive thickener, phthalocyanine material, silicate material, wetting agent and water;
the solid electrolyte, the water-based adhesive thickener, the phthalocyanine salt material, the silicate material and the wetting agent are in a mass ratio of 90-110: 3-10: 0.01-0.05: 0.01 to 0.02:0.05 to 0.15.
Preferably, the solid content of the aqueous solid electrolyte slurry is 10% -40%.
Preferably, the phthalocyanine salt material comprises at least one of copper phthalocyanine, sodium phthalocyanine, aluminum phthalocyanine chloride, zinc phthalocyanine, nickel phthalocyanine, magnesium phthalocyanine and dilithium phthalocyanine;
the copper phthalocyanine is beta-crystal copper phthalocyanine;
the particle size range of the phthalocyanine salt material is 20-100 nm, and D50 is less than or equal to 80 and nm.
Preferably, the silicate material includes at least one of lithium silicate, lithium metasilicate, lithium hexafluorosilicate and sodium magnesium lithium silicate.
Preferably, the solid electrolyte comprises Li 1+x Al x Ti 2-x (PO 4 ) 3 (0 < x < 2) or Li 3y La 2/(3-y) TiO 3 （0<y<0.167）。
Preferably, the aqueous binding thickener comprises at least one of carboxymethyl acrylate, carboxymethyl cellulose salt, alginate, xanthan gum, acrylonitrile copolymer, acrylic water-based adhesive, polyacrylamide-based adhesive, polyacrylate-based adhesive, polyvinyl alcohol-based adhesive, and alkoxy-based terpolymer.
Preferably, the wetting agent comprises at least one of an acetylenic diol wetting agent, a polyether siloxane wetting agent and an isopropyl alcohol wetting agent.
The invention also provides a preparation method of the aqueous solid electrolyte slurry, which comprises the following steps:
a1 Mixing phthalocyanine salt material and solid electrolyte to obtain powder A;
mixing a first part of water with silicate materials to obtain slurry B;
a2 Mixing the powder A and the slurry B to obtain a slurry C;
a3 Mixing the aqueous adhesive thickener with the slurry C to obtain slurry D;
a4 After the wetting agent and the slurry D are mixed, adding a second part of water to adjust the solid content, thus obtaining the water-based solid electrolyte slurry.
The invention also provides a solid electrolyte membrane, which is characterized by comprising:
a base film;
a coating layer composited on the surface of the base film;
the coating is prepared from the aqueous solid electrolyte slurry described above; or prepared from the aqueous solid electrolyte slurry prepared by the preparation method described above.
The present invention also provides a secondary battery in which the separator is the solid electrolyte separator described above.
The invention provides an aqueous solid electrolyte slurry, comprising: solid electrolyte, water-based adhesive thickener, phthalocyanine material, silicate material, wetting agent and water; the solid electrolyte, the water-based adhesive thickener, the phthalocyanine salt material, the silicate material and the wetting agent are in a mass ratio of 90-110: 3-10: 0.01-0.05: 0.01 to 0.02:0.05 to 0.15. The invention solves the stability problem of the solid electrolyte in the aqueous solution, and can obviously improve the ion precipitation problem of the solid electrolyte in the aqueous solution through the composite use of the phthalocyanine salt material and the silicate salt material. In the aspect of slurry, the practical problems of slurry gelation, agglomeration and the like caused by the pH change of the slurry due to ion precipitation can be improved, so that the practical performance and practical value of the slurry are improved, and the practical industrial effect of the invention is ensured. The problems of structural damage and poor ionic conductivity of the solid electrolyte caused by ion precipitation of the solid electrolyte can be improved in the aspect of the battery, so that the electrochemical performance (such as the internal resistance and the cycle performance of the battery) of the solid electrolyte in the battery can be better improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an aqueous solid electrolyte slurry, comprising: solid electrolyte, water-based adhesive thickener, phthalocyanine material, silicate material, wetting agent and water;
the solid electrolyte, the water-based adhesive thickener, the phthalocyanine salt material, the silicate material and the wetting agent are in a mass ratio of 90-110: 3-10: 0.01-0.05: 0.01 to 0.02:0.05 to 0.15.
The solid content of the aqueous solid electrolyte slurry is 10% -40%, such as 10%, 18%, 20%, 25%, 28%, 30%, 35%, 38%, 40%.
In certain embodiments of the present invention, the solid state electrolyte comprises Li 1+x Al x Ti 2-x (PO 4 ) 3 (0 < x < 2) or Li 3y La 2/(3-y) TiO 3 （0<y<0.167 A) is provided; specifically, the solid electrolyte is Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 、Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 、Li 1.1 Al 0.1 Ti 1.9 (PO 4 ) 3 、Li 2.5 Al 1.5 Ti 0.5 (PO 4 ) 3 Or Li (lithium) 0.3 La 0.69 TiO 3 . Can be generally commercially available.
In certain embodiments of the present invention, the aqueous binding thickener comprises at least one of carboxymethyl acrylate, carboxymethyl cellulose salt, alginate, xanthan gum, acrylonitrile copolymer, acrylic water-based adhesive, polyacrylamide-based adhesive, polyacrylate-based adhesive, polyvinyl alcohol-based adhesive, and alkoxy-based terpolymer; the acrylonitrile copolymer may be acrylonitrile copolymer LA133; the polyacrylate binder may be GR-401B.
According to the invention, through the composite use of the phthalocyanine salt material and the silicate material, the performance loss caused by ion precipitation of the solid electrolyte material in the aqueous solution can be effectively improved.
In certain embodiments of the present invention, the phthalocyanine salt material comprises at least one of copper phthalocyanine, sodium phthalocyanine, aluminum phthalocyanine chloride, zinc phthalocyanine, nickel phthalocyanine, magnesium phthalocyanine, and dilithium phthalocyanine; the phthalocyanine salt material is mainly used for surface coating of a solid electrolyte main material, and isolating interface contact between the solid electrolyte material and water to reduce ion precipitation of the material so as to achieve the protection effect on the solid electrolyte.
Preferably, the phthalocyanine salt material is copper phthalocyanine. According to the invention, copper phthalocyanine is preferably used as a main material protective agent, so that side reactions are not generated in a slurry aqueous solution system and a battery electrolyte system, and the use requirement of the battery system is met.
Preferably, the copper phthalocyanine is beta-crystal form copper phthalocyanine. The invention further selects beta crystal form copper phthalocyanine, which can better match with silicate materials to further improve the improvement effect.
The particle size range of the phthalocyanine salt material is preferably 20-100 nm, and D50 is less than or equal to 80 and nm; preferably, d50.ltoreq.50 nm, such as d50=42 nm, 43 nm, 47 nm or 80 nm. The phthalocyanine salt material needs to be coated on the surface of the solid electrolyte to act, and the particle size of the phthalocyanine salt material is further limited, so that the coating effect of the phthalocyanine salt material can be effectively improved.
In certain embodiments of the present invention, the silicate-based material comprises at least one of lithium silicate, lithium metasilicate, lithium hexafluorosilicate, and lithium sodium magnesium silicate; the silicate material is mainly used for increasing the concentration of lithium ions in the solution so as to achieve the condition of ion saturation to inhibit the precipitation of lithium ions of the main material, and the problem of ion precipitation of the solid electrolyte in the solution is remarkably improved through the combined action of the phthalocyanine material and the silicate material.
Preferably, the silicate material is lithium silicate. According to the invention, lithium silicate is preferably used as an ion precipitation inhibitor, lithium ions are firstly dissolved in a solution to precipitate lithium ions so as to inhibit the precipitation of lithium ions in a subsequent solid electrolyte, then silicate can react with hydrofluoric acid to generate materials such as silicon fluoride and the like in the subsequent battery production process, the hydrofluoric acid in the battery is consumed, the corrosion of the hydrofluoric acid on the battery is reduced, and meanwhile, the silicon fluoride generated by the reaction can also participate in the generation of a SEI film of the battery, so that the consumption of lithium ions of the positive electrode of the battery is reduced, and the battery capacity is improved.
In some embodiments of the invention, the lithium silicate can be lithium polysilicate, has good water-resistant and hydrophobic effects, and is beneficial to reducing the water content of a product coating, so that the water and electrolyte are reduced to generate hydrofluoric acid, and the influence on the battery performance is reduced. Preferably, the lithium polysilicate comprises lithium disilicate, such as Li 6 Si 2 O 7 Or 3Li 2 O·2SiO 2 、Li 2 Si 2 O 5 Or Li (lithium) 2 O·2SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Or include lithium pentasilicate, e.g. Li 2 Si 5 O 11 Or Li (lithium) 2 O·5SiO 2 。
In certain embodiments of the present invention, the wetting agent comprises at least one of an acetylenic diol wetting agent, a polyether siloxane wetting agent, and an isopropyl alcohol wetting agent. Specifically, the polyether siloxane wetting agent is a TEGOPREN 5840 surfactant wetting agent, and the alkyne diol wetting agent is GREESOL DP1060H.
In certain embodiments of the invention, the water is deionized water.
In certain embodiments of the present invention, the mass ratio of the solid electrolyte, the aqueous binding thickener, the phthalocyanine salt material, the silicate material, and the wetting agent is 100:5:0.03:0.01:0.1, 100:5:0.05:0.01:0.1, 100:5:0.02:0.01:0.1, 100:5:0.01:0.01:0.1, 100:5:0.03:0.02:0.1 or 100:9:0.03:0.01:0.1.
the invention also provides a preparation method of the aqueous solid electrolyte slurry, which comprises the following steps:
a1 Mixing phthalocyanine salt material and solid electrolyte to obtain powder A;
mixing a first part of water with silicate materials to obtain slurry B;
a2 Mixing the powder A and the slurry B to obtain a slurry C;
a3 Mixing the aqueous adhesive thickener with the slurry C to obtain slurry D;
a4 After the wetting agent and the slurry D are mixed, adding a second part of water to adjust the solid content, thus obtaining the water-based solid electrolyte slurry.
In certain embodiments of the invention, the mixing is uniform.
In some embodiments of the present invention, the mass concentration of the slurry B is 0.01% -5.00%.
In some embodiments of the invention, the second portion of water is added to adjust the solids content to 10% -40%.
According to the invention, the main material and the phthalocyanine salt material are mixed preferentially, so that the optimal coating effect can be ensured, and the consistency state and stability of slurry output are ensured.
In the invention, the aqueous solid electrolyte slurry is used for preparing a coating on the surface of a base film in a solid electrolyte membrane.
The present invention also provides a solid electrolyte separator comprising:
a base film;
a coating layer composited on the surface of the base film;
the coating is prepared from the aqueous solid electrolyte slurry described above; or prepared from the aqueous solid electrolyte slurry prepared by the preparation method described above.
In certain embodiments of the invention, the base film comprises a PE film, a PE film surface coated with a ceramic coating, a PP film surface coated with a ceramic coating, or a nonwoven film.
The thickness of the base film is 5-20 mu m.
In some embodiments of the invention, the thickness of the coating is 0.5-5 μm.
The invention also provides a preparation method of the solid electrolyte membrane, which comprises the following steps:
and uniformly coating the aqueous solid electrolyte slurry on the surface of the base film, and curing to obtain the solid electrolyte diaphragm.
The surface includes upper and lower surfaces of the base film.
The method of curing may be drying.
The present invention also provides a secondary battery in which the separator is the solid electrolyte separator described above, or the solid electrolyte separator manufactured by the manufacturing method described above.
Specifically, the secondary battery includes a positive electrode, a negative electrode, a separator, and an electrolyte; the separator is the solid electrolyte separator described above, or the solid electrolyte separator produced by the production method described above.
In some embodiments of the present invention, the method for preparing the positive electrode includes the steps of:
b1 Uniformly mixing an anode active material, a conductive agent, a dispersing agent, a binder and NMP to obtain anode slurry;
b2 Uniformly coating the positive electrode slurry on two surfaces of a positive electrode current collector, and carrying out cold pressing and slitting on the obtained film layer after drying to obtain the positive electrode plate.
In step b 1):
in certain embodiments of the invention, the positive electrode active material is lithium iron phosphate; the conductive agent is conductive carbon black; the binder is polyacrylic acid (PAA) or a salt binder thereof; the mass ratio of the positive electrode active material to the conductive agent to the dispersant to the binder to the NMP is 96:1:0.6:0.6:1.8.
the mixing is stirring and mixing.
In step b 2):
in some embodiments of the invention, the thickness of the coating is 95-105 [ mu ] m.
The positive current collector is aluminum foil.
In some embodiments of the present invention, the method for preparing the negative electrode includes the steps of:
c1 Uniformly mixing a negative electrode active material, a conductive agent, a binder, a thickener and a solvent to obtain a negative electrode slurry;
c2 Uniformly coating the negative electrode slurry on two surfaces of a negative electrode current collector, and carrying out cold pressing and slitting on the obtained film layer after drying to obtain a negative electrode plate.
In step c 1):
in certain embodiments of the present invention, the negative electrode active material is artificial graphite, the conductive agent is conductive carbon black, the binder is Styrene Butadiene Rubber (SBR), the thickener is sodium hydroxymethyl cellulose (CMC), and the solvent is deionized water. The mass ratio of the anode active material to the conductive agent to the binder to the thickener is 96.2:0.8:0.8:1.2.
in step c 2):
in some embodiments of the invention, the thickness of the coating is 105-115 μm.
The negative current collector is copper foil.
In certain embodiments of the present invention, the electrolyte is LiPF 6 A solution, wherein the solvent comprises Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) in a volume ratio of 3:7, preparing a base material; the LiPF is 6 The mass concentration of the solution was 12.5%.
The invention also provides a preparation method of the secondary battery, which comprises the following steps:
sequentially stacking and winding the positive electrode plate, the diaphragm and the negative electrode plate to obtain an electrode assembly;
and placing the electrode assembly into an outer package, adding electrolyte, packaging, standing, forming and aging to obtain the secondary battery.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
According to the invention, through the composite use of the phthalocyanine salt material and the silicate material, the structural stability of the solid electrolyte material (conductive ceramic) in the aqueous solution can be well protected from the formula level by matching with other components, so that the structural stability of the solid electrolyte in the slurry is ensured, the ion conductivity performance loss of the solid electrolyte is reduced, and the expected effect of the high ion conductivity function of the solid electrolyte (conductive ceramic) is ensured to be exerted after the solid electrolyte is put into practical production.
In the aqueous solid electrolyte slurry provided by the invention, the phthalocyanine material and the silicate material are adopted at the same time, and the phthalocyanine material and the silicate material have good compatibility with the aqueous adhesive thickener and the wetting agent. The invention further defines the components of the aqueous binding thickener and wetting agent, which helps to improve the electrochemical performance of the secondary battery.
The technical scheme provided by the invention can neutralize hydrofluoric acid in the battery, reduce corrosion of the hydrofluoric acid to the lithium ion battery, improve the cycle performance and the safety performance of the battery, reduce consumption reaction of the hydrofluoric acid to lithium ions (reaction generates lithium oxide and lithium fluoride) and ensure the energy density of the lithium battery.
In order to further illustrate the present invention, the following examples are provided to describe in detail an aqueous solid electrolyte slurry, a solid electrolyte separator and a secondary battery according to the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
1) Preparation of a solid electrolyte separator:
1-1) in an aqueous solid electrolyte slurry,
100 parts by weight of a solid electrolyte;
5 parts by weight of an aqueous adhesive thickener;
0.03 parts by weight of copper phthalocyanine;
0.01 parts by weight of lithium silicate;
0.1 part by weight of wetting agent.
The solid electrolyte is Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 。
The above formula is the mass ratio of all substances in the aqueous solid electrolyte slurry after removing water, and the addition amount of deionized water is converted and added according to the solid content of the aqueous slurry in the following examples.
In this example, CAS number of copper phthalocyanine: 147-14-8, beta-type, >90.0%, available from Shanghai Ala Biotechnology Co., ltd., particle size range 20-100 nm, D50=42 nm; CAS number of lithium silicate: 10102-24-6, modulus 4.8, available from Shanghai Ala Biotechnology Co., ltd; the aqueous adhesive thickener was an acrylonitrile copolymer LA133, available from sienna technology limited; the wetting agent is polyether siloxane wetting agent, and is modified organosilicon surface active wetting agent with low foam of TEGOPREN 5840;
a method of preparing an aqueous solid electrolyte slurry (stepwise mixing) comprising:
1-1-1) uniformly mixing copper phthalocyanine and a solid electrolyte to obtain powder A;
uniformly mixing a first part of deionized water with lithium silicate to obtain slurry B with the mass concentration of 3%;
1-1-2) uniformly mixing the powder A and the slurry B to obtain slurry C;
1-1-3) uniformly mixing the water-based adhesive thickener and the slurry C to obtain slurry D;
1-1-4) uniformly mixing a wetting agent and the slurry D, and then adding a second part of deionized water to adjust the solid content to 25% to obtain the aqueous solid electrolyte slurry.
1-2) uniformly coating aqueous solid electrolyte slurry on the upper and lower surfaces of a base film (PE film, thickness of 9 mu m), and drying to obtain a solid electrolyte membrane (the thickness of a coating in the solid electrolyte membrane is 2 mu m).
2) Preparation of positive electrode:
2-1) positive electrode active material (lithium iron phosphate), conductive agent (conductive carbon black), dispersant, binder (PAA) and NMP were mixed in a mass ratio of 96:1:0.6:0.6:1.8, stirring and uniformly mixing to obtain positive electrode slurry;
2-2) uniformly coating the positive electrode slurry on two surfaces of a positive electrode current collector aluminum foil, wherein the thickness of the coating is 100 mu m, and after drying, cold pressing and slitting the obtained film layer to obtain a positive electrode plate.
3) Preparation of the negative electrode:
3-1) uniformly mixing a negative electrode active material (artificial graphite), a conductive agent (conductive carbon black), a binder (SBR), a thickening agent (CMC) and a solvent (deionized water) to obtain a negative electrode slurry;
3-2) uniformly coating the negative electrode slurry on two surfaces of a negative electrode current collector copper foil, wherein the thickness of the coating is 110 mu m, and after drying, cold pressing and slitting the obtained film layer to obtain a negative electrode plate.
4) Preparation of secondary battery:
4-1) stacking and winding the positive electrode plate, the solid electrolyte membrane and the negative electrode plate in sequence to obtain an electrode assembly;
4-2) placing the electrode Assembly in an external packaging, adding electrolyte (LiPF) 6 A solution, wherein the solvent comprises Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) in a volume ratio of 3:7, preparing a base material; the LiPF is 6 The mass concentration of the solution is 12.5%), and the secondary battery is prepared through packaging, standing, formation and aging.
Example 2
The difference from example 1 is that:
step 1-1), the weight part of copper phthalocyanine in the aqueous solid electrolyte slurry is 0.05 part.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 3
The difference from example 1 is that:
step 1-1), wherein in the aqueous solid electrolyte slurry, the weight part of copper phthalocyanine is 0.02 part;
the particle size of copper phthalocyanine ranges from 20 to 100 nm, d50=47 nm.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 4
The difference from example 1 is that:
step 1-1), the weight part of lithium silicate in the aqueous solid electrolyte slurry is 0.02 part.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 5
The difference from example 1 is that:
step 1-1), the weight part of copper phthalocyanine in the aqueous solid electrolyte slurry is 0.01 part.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Comparative example 1
The difference from example 1 is that:
step 1-1), the weight part of copper phthalocyanine in the aqueous solid electrolyte slurry is 0 part, and the weight part of lithium silicate is 0 part.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Comparative example 2
The difference from example 1 is that:
step 1-1), wherein the weight part of copper phthalocyanine in the aqueous solid electrolyte slurry is 0 part.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Comparative example 3
The difference from example 4 is that:
step 1-1), wherein the weight part of copper phthalocyanine in the aqueous solid electrolyte slurry is 0 part.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Comparative example 4
The difference from example 1 is that:
step 1-1), the weight part of copper phthalocyanine in the aqueous solid electrolyte slurry is 0 part, and the weight part of lithium silicate is 0.04 part.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Comparative example 5
The difference from example 1 is that:
step 1-1), the weight part of lithium silicate in the aqueous solid electrolyte slurry is 0 part.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Comparative example 6
The difference from example 2 is that:
step 1-1), the weight part of lithium silicate in the aqueous solid electrolyte slurry is 0 part.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 6
The difference from example 1 is that:
the particle size range of copper phthalocyanine is 20-100 nm, d50=80 nm.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 7
The difference from example 1 is that:
copper phthalocyanine is epsilon-copper phthalocyanine;
particle size range is 20-100 nm, d50=43 nm;
finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 8
The difference from example 1 is that:
replacing copper phthalocyanine with sodium phthalocyanine;
particle size range is 20-100 nm, d50=43 nm;
finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 9
The difference from example 1 is that:
replacing copper phthalocyanine with magnesium phthalocyanine;
finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 10
The difference from example 1 is that:
replacing copper phthalocyanine with aluminum phthalocyanine chloride;
finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 11
The difference from example 1 is that:
replacing copper phthalocyanine with zinc phthalocyanine;
finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 12
The difference from example 1 is that:
replacing lithium silicate with lithium metasilicate;
finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 13
The difference from example 1 is that:
replacing lithium silicate with lithium hexafluorosilicate;
finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 14
The difference from example 1 is that:
replacing lithium silicate with sodium magnesium lithium silicate;
finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Comparative example 7
The difference from example 1 is (the amount of wetting agent is different):
the weight portion of the wetting agent is 0.01 portion.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Comparative example 8
The difference from example 1 is (the amount of wetting agent is different):
the weight portion of the wetting agent is 0.3 portion.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 15
The difference from example 1 is (the amount of aqueous binding thickener is different):
the weight portion of the aqueous cohesive thickening agent is 9 portions.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 16
The difference from example 1 is (the components of the aqueous binding thickener are different):
the aqueous binding thickener is selected from GR-401B (henna gakuri electric materials limited).
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 17
The difference from example 1 is (the components of the wetting agent are different):
the wetting agent is selected from green DP1060H (yueyang kemen underwater aids limited).
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 18
The difference from example 1 is that:
step 1-1) solid electrolyte is composed of Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 Change to Li 0.3 La 0.69 TiO 3 。
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 19
The difference from example 1 is that:
step 1-1) solid electrolyte is composed of Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 Change to Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 。
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 20
The difference from example 1 is that:
step 1-1) solid electrolyte is composed of Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 Change to Li 1.1 Al 0.1 Ti 1.9 (PO 4 ) 3 。
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 21
The difference from example 1 is that:
step 1-1) solid electrolyte is composed of Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 Change to Li 2.5 Al 1.5 Ti 0.5 (PO 4 ) 3 。
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Example 22
The difference from example 1 is that:
by changing the amount of the second portion of water, the solid content of the aqueous solid electrolyte slurry finally obtained was changed from 25% to 10%, and a secondary battery was produced.
Example 23
The difference from example 1 is that:
by changing the amount of the second portion of water, the solid content of the aqueous solid electrolyte slurry finally obtained was changed from 25% to 18%, and a secondary battery was produced.
Example 24
The difference from example 1 is that:
by changing the amount of the second portion of water, the solid content of the aqueous solid electrolyte slurry finally obtained was changed from 25% to 40%, and thus a secondary battery was produced.
Comparative example 9
The difference from example 1 is that:
a method for preparing an aqueous solid electrolyte slurry comprising:
copper phthalocyanine, solid electrolyte, lithium silicate, an aqueous adhesive thickener, a wetting agent and deionized water are directly mixed until uniform, so as to obtain aqueous solid electrolyte slurry with the solid content of 25%, and further obtain the secondary battery.
Comparative example 10
The difference from example 1 is (the components of the aqueous binding thickener are different):
the water-based adhesive thickener is sodium polyacrylate adhesive with the molecular weight of 30-35 ten thousand and the net content of more than or equal to 99.0%.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
Comparative example 11
The difference from example 1 is (the components of the wetting agent are different):
the wetting agent is selected from isopropanol.
Finally, an aqueous solid electrolyte slurry having a solid content of 25% was obtained, and a secondary battery was produced.
The performances of the secondary batteries of examples 1 to 24 and comparative examples 1 to 11 were compared, and the results are shown in table 1. Wherein, R1: the mass ratio of the phthalocyanine salt material (coating agent) to the solid electrolyte; r2: silicate material (inhibitor) to solid electrolyte mass ratio.
The main decision criteria are battery level data, slurry level as reference.
In theory, the coating effect is best represented by measuring the amount of precipitated lithium ions, but the added inhibitor lithium silicate also contains lithium ions, which interfere with the test data, so the titanium ion precipitation in the test solution is used as a comparison.
In particular, the method comprises the steps of,
measurement of the direct current impedance of the battery: the secondary battery was charged to 3.65V at a constant current of 1/3C at 25 ℃, and then charged to 0.05C at a constant voltage of 3.65V, and after standing for 5min, the voltage V1 was recorded. Then, the voltage V2 was recorded by discharging at 1/3C for 30 s. Calculating the direct current impedance of the battery according to the formula (1):
battery dc impedance= (V2-V1)/(1/3C) (1).
Measurement of battery capacity retention: charging the secondary battery at 25deg.C under constant current of 1/3C to 3.65V, charging at constant voltage of 3.65V to current of 0.05C, standing for 5min, discharging at 1/3C to 2.7V, and recording the measured discharge capacity as initial capacity C 0 . Repeating the above steps for the same battery, andat the same time, the discharge capacity C of the battery after n times of circulation is recorded n Battery capacity retention rate P after n cycles n Calculated according to formula (2):
P n =100%×C n /C 0 （2）。
wherein the first cycle corresponds to n=1, the second cycle corresponds to n=2. The battery capacity retention after 500 cycles was measured.
Other test items were tested according to the general method.
The shipment time is 1h after the solid electrolyte slurry is prepared.
Table 1 performance and related parameters of secondary batteries of examples 1 to 24 and comparative examples 1 to 11
Table 1 (Xuebiao Yi)
Table 1 (Xuebiao)
As can be seen from table 1:
example 2 and example 4 demonstrate that increasing the additive mass does not optimize the cell performance more than example 1, and that too much addition adversely affects the performance of the solid state electrolyte.
Example 3 and example 5 demonstrate that reducing the adjuvant quality compared to example 1 affects optimal performance.
Comparative example 2 illustrates the effectiveness of the coating agent, compared to example 1, the absence of the coating agent, the significant precipitation of solid electrolyte ions, and severe structural damage, resulting in increased dc resistance, affecting gram capacity and cycle performance.
In comparison with example 1, comparative example 3 and comparative example 4 show that the effect of compounding the two cannot be achieved by simply adding an inhibitor.
Compared with example 1, comparative example 5 and comparative example 6 demonstrate the effectiveness of the inhibitor, lack of the inhibitor, relatively increased precipitation of solid electrolyte ions, increased moisture, poor neutralization of hydrofluoric acid, resulting in reduced gram capacity, and simultaneous effect on cycle performance, while also demonstrating that the addition of the capping agent alone does not achieve the effect of the combination of both.
Compared with example 1, example 6 shows that the coating agent with larger particle size has a smaller coating effect on the main material than that of the main material, so that more ions of the main material are precipitated, and the pH stability of the solution and the battery performance are affected.
Compared with example 1, example 7 shows that the coating agents with different crystal forms are selected, the absolute value difference of the pH change of the solution for 24 hours is increased, the stability of the coating agents with other crystal forms is not as good as that of the beta type, and meanwhile, the electrochemical reaction of the subsequent battery is influenced due to the insufficient stability of the material, so that the performance of the battery is poor.
Compared with example 1, comparative example 7 shows that sufficient wetting agent is required to ensure the spreading effect of the coating on the surface of the separator, and the wetting agent is less likely to cause the solid electrolyte coating to leak coating, shrink hole and the like, so that the effect of the solid electrolyte coating cannot be effectively exerted.
Example 16, compared to example 1, demonstrates that the use of a different aqueous binding thickener, the compatibility with the system (binding power, air permeability, etc.), and the suitability of the aqueous binding thickener in the electrolyte system (swelling of the material, peeling of the coating, etc.), have different effects on the performance of the battery.
In comparison with example 1, in comparative example 9, the components of the aqueous solid electrolyte slurry are directly mixed, and other auxiliaries interfere with the coating effect of the phthalocyanine salt material on the main material, and interfere with the dispersibility of the main material particles. According to the invention, the optimal effect can be achieved only by forming cladding between the phthalocyanine salt and the solid electrolyte main material, if the phthalocyanine salt and the binder or other auxiliary agents are mixed at the same time, the phthalocyanine salt and the binder or other auxiliary agents can be clustered together, and the solid electrolyte interface can not be clad in a concentrated way; the main material and the phthalocyanine salt material are mixed preferentially, so that the optimal coating effect can be ensured, and the consistency state and stability of slurry output are ensured.
Examples 8 to 11 show that the use of different phthalocyanine-based coating agents can effectively improve the performance of the solid electrolyte in the battery as compared with comparative example 1, but have disadvantages over the preferred example 1.
Comparative example 8 increased the content of the wetting agent compared to example 1, and an excessive amount of the wetting agent may change the surface tension and interface effect of the SEI film at the interface of the electrolyte and the battery in the battery, affecting the electrochemical performance of the battery.
Compared with the example 1, the example 17 and the comparative example 11 adopt different wetting agents, and the improper wetting agents (such as the comparative example 11) are adopted to cause poor spreading effect of the slurry on the diaphragm, so that the problems of missing coating, shrinkage cavity and the like can occur, and the effect exertion of the solid electrolyte is influenced; meanwhile, the separator in the area of the missing coating and shrinkage cavity is not protected by the coating of the solid electrolyte, so that the accelerating voltage and the electrolyte act to generate oxidation-reduction and other changes in the use process of the battery, and the structural function is degraded, so that the battery performance is deteriorated.
Compared with the embodiment 1, the embodiment 18 adopts different solid electrolytes, and the technical scheme provided by the invention can provide better coating and protecting effects for different solid electrolytes from the data point of view, so that the effect of the solid electrolytes is ensured to be optimally exerted.
Examples 19 to 21 are for Li as compared with example 1 1+x Al x Ti 2-x (PO 4 ) 3 The values of x are different from 0 to 2, so that the number of moles of elements in the solid electrolyte is different under the same solid content, but only a trace of ion concentration change is caused, and the battery performance is not obviously affected by the solid electrolyte with different values of x.
Compared with example 1, examples 22-24 adopt different slurry solid contents, and from the data, the solid contents are different, so that the mass solid contents of elements in the solid electrolyte in the slurry are changed, but only trace element concentration changes are caused, and after the coating is actually carried out and dried, the formed coating structure is the same as the components, and after the secondary battery is manufactured, the battery performance is hardly affected.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. An aqueous solid electrolyte slurry comprising: solid electrolyte, water-based adhesive thickener, phthalocyanine material, silicate material, wetting agent and water;
the solid electrolyte, the water-based adhesive thickener, the phthalocyanine salt material, the silicate material and the wetting agent are in a mass ratio of 90-110: 3-10: 0.01-0.05: 0.01 to 0.02: 0.05-0.15;
the phthalocyanine salt material comprises at least one of copper phthalocyanine, sodium phthalocyanine, aluminum phthalocyanine chloride, zinc phthalocyanine, nickel phthalocyanine, magnesium phthalocyanine and dilithium phthalocyanine.
2. The aqueous solid electrolyte slurry according to claim 1, wherein the solid content of the aqueous solid electrolyte slurry is 10% to 40%.
3. The aqueous solid electrolyte slurry according to claim 1, wherein the copper phthalocyanine is beta-crystal form copper phthalocyanine;
the particle size range of the phthalocyanine salt material is 20-100 nm, and D50 is less than or equal to 80 and nm.
4. The aqueous solid electrolyte slurry of claim 1, wherein the silicate-based material comprises at least one of lithium silicate, lithium metasilicate, lithium hexafluorosilicate, and sodium magnesium lithium silicate.
5. The aqueous solid electrolyte slurry according to claim 1, wherein the solid electrolyte comprises Li 1+ x Al x Ti 2-x (PO 4 ) 3 （0<x<2) Or Li (lithium) 3y La 2/(3-y) TiO 3 （0<y<0.167）。
6. The aqueous solid electrolyte slurry of claim 1 wherein the aqueous binding thickener comprises at least one of carboxymethyl acrylate, carboxymethyl cellulose salt, alginate, xanthan gum, acrylonitrile copolymer, acrylic water-based binder, polyacrylamide-based binder, polyacrylate-based binder, polyvinyl alcohol-based binder, and alkoxy-based terpolymer.
7. The aqueous solid electrolyte slurry of claim 1, wherein the wetting agent comprises at least one of an acetylenic diol wetting agent, a polyether siloxane wetting agent, and an isopropyl alcohol wetting agent.
8. A method for producing the aqueous solid electrolyte slurry according to any one of claims 1 to 7, comprising the steps of:
a1 Mixing phthalocyanine salt material and solid electrolyte to obtain powder A;
mixing a first part of water with silicate materials to obtain slurry B;
a2 Mixing the powder A and the slurry B to obtain a slurry C;
a3 Mixing the aqueous adhesive thickener with the slurry C to obtain slurry D;
a4 After the wetting agent and the slurry D are mixed, adding a second part of water to adjust the solid content, thus obtaining the water-based solid electrolyte slurry.
9. A solid electrolyte separator, comprising:
a base film;
a coating layer composited on the surface of the base film;
the coating is prepared from the aqueous solid electrolyte slurry according to any one of claims 1 to 7; or from the aqueous solid electrolyte slurry produced by the production method according to claim 8.
10. A secondary battery, characterized in that a separator in the secondary battery is the solid electrolyte separator according to claim 9.
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