CN115275371A - High-temperature-resistant storage lithium ion storage battery with emergency starting power supply and preparation method thereof - Google Patents

High-temperature-resistant storage lithium ion storage battery with emergency starting power supply and preparation method thereof Download PDF

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Publication number
CN115275371A
CN115275371A CN202211042916.4A CN202211042916A CN115275371A CN 115275371 A CN115275371 A CN 115275371A CN 202211042916 A CN202211042916 A CN 202211042916A CN 115275371 A CN115275371 A CN 115275371A
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lithium ion
slurry
power supply
starting power
emergency starting
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王红梅
谈健
杨廷明
张妙
芦金海
陈福成
罗新耀
吴爱深
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Shida Battery Technology Co Ltd
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Shida Battery Technology Co Ltd
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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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • 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

Abstract

The invention relates to the technical field of lithium ion storage batteries, in particular to a high-temperature storage resistant lithium ion storage battery with an emergency starting power supply and a preparation method thereof. A preparation method of a high-temperature storage resistant lithium ion storage battery with an emergency starting power supply comprises the following steps: step A, coating anode slurry on the surface of an aluminum foil, rolling and die-cutting to obtain an anode plate, wherein the anode slurry comprises, by weight, 91-94% of an NCM ternary material, 1-3% of conductive carbon black, 1-3% of super conductive carbon black and 2-3% of a binder; and step B, coating the negative electrode slurry on the surface of the copper foil, and rolling and die cutting to obtain the negative electrode piece. The preparation method of the high-temperature storage resistant emergency starting power supply lithium ion storage battery has the advantages that the prepared high-temperature storage resistant emergency starting power supply lithium ion storage battery has excellent multiplying power starting performance and excellent high-temperature storage performance, the use safety is effectively improved, and the technical problem that the conventional lithium ion storage battery cannot resist high-temperature storage is solved.

Description

High-temperature-resistant storage lithium ion storage battery with emergency starting power supply and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion storage batteries, in particular to a high-temperature storage resistant lithium ion storage battery with an emergency starting power supply and a preparation method thereof.
Background
The lithium ion storage battery is a battery system with better comprehensive performance at present, and is widely applied to an emergency starting power supply at present, but the high-temperature storage performance of the lithium ion storage battery of the current emergency starting power supply is poorer, the lithium ion storage battery of the current emergency starting power supply is stored for 4H at the high temperature of 80 ℃ or stored for 7 days at the temperature of 65 ℃, the battery can bulge, great use safety risks are realized, the potential safety hazard can be caused when the battery is transported or stored at the outdoor high temperature, the use safety is low, and the application field range of the battery is influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a high-temperature storage resistant emergency starting power supply lithium ion storage battery, and the prepared high-temperature storage resistant emergency starting power supply lithium ion storage battery has excellent multiplying power starting performance and excellent high-temperature storage performance, effectively improves the use safety, and solves the technical problem that the conventional lithium ion storage battery cannot resist high-temperature storage.
The invention also aims to provide the lithium ion storage battery with the high-temperature storage resistant emergency starting power supply, which is prepared by the preparation method of the lithium ion storage battery with the high-temperature storage resistant emergency starting power supply, and has the characteristics of good starting performance, excellent high-temperature storage performance, high safety and wide application.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-temperature storage resistant lithium ion storage battery with an emergency starting power supply comprises the following steps:
step A, coating anode slurry on the surface of an aluminum foil, rolling and die-cutting to obtain an anode plate, wherein the anode slurry comprises, by weight, 91-94% of an NCM ternary material, 1-3% of conductive carbon black, 1-3% of super conductive carbon black and 2-3% of a binder;
b, coating the negative electrode slurry on the surface of copper foil, rolling and die-cutting to obtain a negative electrode plate, wherein the raw materials of the negative electrode slurry comprise 92-95% of artificial graphite, 2-4% of a conductive agent, 1-2% of carboxymethyl cellulose and 1-2% of butadiene styrene rubber glue solution according to weight percentage;
step C, combining the positive pole piece, the negative pole piece and the diaphragm in a lamination mode, injecting electrolyte into the battery cell after packaging, and preparing the high-temperature storage-resistant emergency starting power supply lithium ion storage battery after formation, sealing and capacity grading in sequence;
the electrolyte is obtained by mixing ethylene carbonate and ethyl methyl carbonate, and a sulfur-containing high-temperature additive and a lithium salt are added into the electrolyte.
More specifically, in the step C, the electrolyte is obtained by mixing ethylene carbonate and ethyl methyl carbonate according to a mass ratio of 3 2 F 2 、LiPF 6 And LiFSI.
Furthermore, the electrolyte is added with 2 to 5 percent of 1, 3-propane sultone, 0.5 to 1.5 percent of vinyl sulfate and LiPO according to the percentage of the total weight of the electrolyte 2 F 2 0.2～0.5％、LiPF 6 0.5 to 1.0 percent and LiFSI0.5 to 1.0 percent.
Further, in the step a, before the positive electrode slurry is coated on the surface of the aluminum foil, a step of blending the positive electrode slurry is further included, and the step of blending the positive electrode slurry includes:
according to the raw material formula, uniformly mixing a binder and a solvent according to the solid content of 7-10% to prepare a positive binder glue solution, and uniformly mixing conductive carbon black, super conductive carbon black and the solvent according to the solid content of 5-10% to prepare a positive conductive agent slurry; and mixing the positive adhesive glue solution and the positive conductive agent slurry under vacuum for 100-150 min, and then adding the NCM ternary material to prepare the positive slurry.
In step a, the thickness of the aluminum foil is 10 to 16 μm.
In the step A, the surface density of the positive electrode slurry coated on the surface of the aluminum foil is 120-160 mg/mm 2 。
Further, in the step B, before the negative electrode slurry is coated on the surface of the copper foil, a step of preparing the negative electrode slurry is further included, and the step of preparing the negative electrode slurry includes:
uniformly mixing carboxymethyl cellulose and deionized water according to a raw material formula and a solid content of 1-2% to prepare a cathode binder glue solution, and uniformly mixing a conductive agent and the deionized water according to a solid content of 40-45% to prepare a cathode conductive agent slurry; mixing the negative electrode binder glue solution and the negative electrode conductive agent slurry under vacuum for 100-150 min, adding artificial graphite, mixing uniformly, adding the styrene butadiene rubber glue solution, and mixing uniformly to obtain the negative electrode slurry.
In the step B, the thickness of the copper foil is 6 to 8 μm.
In addition, in the lithium ion storage battery with the high-temperature storage resistant emergency starting power supply, the capacity excess ratio of the negative electrode to the positive electrode is 1.08-1.20.
The high-temperature storage resistant emergency starting power supply lithium ion storage battery is prepared by the preparation method of the high-temperature storage resistant emergency starting power supply lithium ion storage battery.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
according to the invention, an NCM ternary material, conductive carbon black, super conductive carbon black and a binder are used in positive electrode slurry, artificial graphite, a conductive agent, carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR) glue solution are used in negative electrode slurry, the electrolyte is obtained by mixing Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC), a sulfur-containing high-temperature additive and lithium salt are added in the electrolyte, when the positive electrode, the negative electrode and the electrolyte are matched, the high-purity conductive carbon black, the unique branched chain and the super conductive carbon black in a polycrystalline allowable form in the positive electrode are fully contacted with active substance particles to form a high-efficiency conductive network, a composite lithium salt system matched with the electrolyte can meet the high-rate discharge performance of the battery, and meanwhile, the sulfur-containing high-temperature additive is added in the electrolyte formula, so that the gas production problem of the NCM battery under high-temperature storage can be fully inhibited, the technical problem that the existing lithium ion storage battery cannot be subjected to high-temperature storage is solved, the lithium ion storage battery with the high-temperature storage emergency starting power supply has excellent rate starting performance, can meet 180C discharge 3S, and has excellent high-temperature storage performance, 48H or 65 ℃ storage at high temperature storage temperature of 48H or 65 ℃, cannot be expanded for storage for 1 month, and the lithium ion battery cannot be widely used in the outdoor, and the safety condition can be improved.
Drawings
FIG. 1 is a graph of a test of 180C discharge 3S for example one of the present invention and a comparative example (conventional cell);
FIG. 2 is a graph of the rate of change of thickness measured at 80 ℃ for high temperature storage of examples one and comparative examples (conventional cells) of the present invention;
FIG. 3 is a graph of a thickness rate test for high temperature 65 ℃ storage of example one of the present invention and a comparative example (conventional cell);
FIG. 4 is a graph of a test of 180C discharge 3S for example two of the present invention and a comparative example (conventional cell);
FIG. 5 is a graph of a thickness change rate test at high temperature 80 ℃ for example two of the present invention and a comparative example (conventional battery);
fig. 6 is a graph of a thickness change rate test of inventive example two and a comparative example (conventional battery) stored at a high temperature of 65 ℃.
Detailed Description
A preparation method of a high-temperature storage resistant lithium ion storage battery with an emergency starting power supply comprises the following steps:
step A, coating anode slurry on the surface of an aluminum foil, rolling and die-cutting to obtain an anode plate, wherein the anode slurry comprises, by weight, 91-94% of an NCM ternary material, 1-3% of conductive carbon black, 1-3% of super conductive carbon black and 2-3% of a binder;
b, coating the negative electrode slurry on the surface of copper foil, rolling and die-cutting to obtain a negative electrode plate, wherein the raw materials of the negative electrode slurry comprise 92-95% of artificial graphite, 2-4% of a conductive agent, 1-2% of carboxymethyl cellulose and 1-2% of styrene-butadiene rubber glue solution according to weight percentage;
step C, combining the positive pole piece, the negative pole piece and the diaphragm in a lamination mode, encapsulating, injecting electrolyte into the battery cell, and sequentially carrying out formation, sealing and capacity grading to obtain the high-temperature storage resistant emergency starting power supply lithium ion storage battery;
the electrolyte is obtained by mixing ethylene carbonate and ethyl methyl carbonate, and a sulfur-containing high-temperature additive and a lithium salt are added into the electrolyte.
According to the invention, an NCM ternary material, conductive carbon black, super conductive carbon black and a binder are used in positive electrode slurry, artificial graphite, a conductive agent, carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR) glue solution are used in negative electrode slurry, the electrolyte is obtained by mixing Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC), a sulfur-containing high-temperature additive and lithium salt are added in the electrolyte, when the positive electrode, the negative electrode and the electrolyte are matched, the high-purity conductive carbon black, the unique branched chain and the super conductive carbon black in a polycrystalline allowable form in the positive electrode are fully contacted with active substance particles to form a high-efficiency conductive network, a composite lithium salt system matched with the electrolyte can meet the high-rate discharge performance of the battery, and meanwhile, the sulfur-containing high-temperature additive is added in the electrolyte formula, so that the gas production problem of the NCM battery under high-temperature storage can be fully inhibited, the technical problem that the existing lithium ion storage battery cannot be subjected to high-temperature storage is solved, the lithium ion storage battery with the high-temperature storage emergency starting power supply has excellent rate starting performance, can meet 180C discharge 3S, and has excellent high-temperature storage performance, 48H or 65 ℃ storage at high temperature storage temperature of 48H or 65 ℃, cannot be expanded for storage for 1 month, and the lithium ion battery cannot be widely used in the outdoor, and the safety condition can be improved.
The term "store 48H at 80" refers to that the lithium ion battery is stored for 48H at 80 ± 2 ℃ after being fully charged, and the storage at 65 ℃ is carried out for 1 month in the same way; the above-mentioned "180C discharges 3S", C denotes a symbol of a discharge rate of the lithium battery, and 180C denotes that the lithium battery discharges 3S at a discharge rate of 180 times.
Furthermore, in the cathode slurry, the NCM multi-component material is 523 nickel cobalt lithium manganate, the dosage of the NCM three-component material is 91-94%, if the dosage of the NCM three-component material is too small, the cathode active material is too low, which results in a low cathode capacity, and if the dosage of the NCM three-component material is too large, the conductive agent or the binder is too small, which affects the starting performance of the battery; the conductive carbon black has the characteristic of high purity, the consumption is 1-3%, if the consumption of the conductive carbon black is too low, the starting performance cannot be met, and if the consumption of the conductive carbon black is too high, the capacity of the positive electrode can be reduced; the super conductive carbon black has unique branched chains and polycrystal allowable forms, the using amount is 1-3%, if the using amount of the super conductive carbon black is too small, the starting performance cannot be met, and if the using amount of the super conductive carbon black is too large, the cost of the battery is high; the binder can be polyvinylidene fluoride (PVDF) binder, the usage amount is 2-3%, if the usage amount of the binder is too small, the powder falling of the pole piece can be caused, the adhesion force is poor, and if the usage amount of the binder is too large, the capacity of the positive pole is too low, the impedance of the pole piece is increased, and the starting performance is influenced.
Further, in the negative electrode slurry, the amount of the artificial graphite is 92 to 95%, if the amount of the artificial graphite is too small, the negative electrode active material is too low, resulting in a low negative electrode capacity, and if the amount of the artificial graphite is too large, resulting in a small amount of the conductive agent or binder, which affects the starting performance; the conductive agent has the characteristic of high purity, the consumption is 2-4%, if the consumption of the conductive agent is too low, the starting performance cannot be met, and if the consumption of the conductive agent is too high, the cost is increased, and particularly, the conductive agent can be conductive carbon black SUPER P Li (SUP-Li for short); the amount of carboxymethyl cellulose (CMC) is 1-2%; if the consumption of the CMC is too small, the pole piece can fall off powder and has poor adhesion, and if the consumption of the CMC is too large, the negative electrode capacity is low, the impedance of the pole piece is increased, and the starting performance is influenced; the dosage of SBR glue solution (SBR glue solution) is 1-2%, if the dosage of SBR glue solution is too small, the pole piece is easy to fall off, the adhesive force is poor, if the dosage of SBR glue solution is too large, the negative electrode capacity is low, the pole piece impedance is increased, and the starting performance is influenced.
More specifically, in the step C, the electrolyte is obtained by mixing ethylene carbonate and ethyl methyl carbonate according to a mass ratio of 3 2 F 2 、LiPF 6 And LiFSI.
The electrolyte adopts a solvent system with high and low temperatures of Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC), wherein the mass ratio of EC to EMC is 3 2 F 2 、LiPF 6 And LiFSI composite lithium salt system to obtain electrolyte; when the anode, the cathode and the electrolyte are matched, the high-purity conductive carbon black of the anode and the super conductive carbon black with unique branched chain and polycrystal allowable forms are fully contacted with active substance particles to formInto a highly efficient conductive network, in cooperation with LiPO 2 F 2 、LiPF 6 And the LiFSI composite lithium salt system can meet the requirement of the high-rate discharge performance of the battery; meanwhile, PS and DTD are used as sulfur-containing high-temperature additives in the electrolyte formula, so that the problem of gas generation of the NCM battery in high-temperature storage can be fully inhibited, and the defect that the NCM battery is not high-temperature-resistant to storage is overcome.
Furthermore, the electrolyte is added with 2 to 5 percent of 1, 3-propane sultone, 0.5 to 1.5 percent of vinyl sulfate and LiPO according to the percentage of the total weight of the electrolyte 2 F 2 0.2～0.5％、LiPF 6 0.5 to 1.0 percent and LiFSI0.5 to 1.0 percent.
By adjusting the usage amount of the sulfur-containing high-temperature additives PS and DTD in the electrolyte, the problem of gas generation of the NCM battery under high-temperature storage can be fully inhibited, and the defect that the battery cannot resist high-temperature storage is overcome. The addition amount of the 1, 3-Propane Sultone (PS) in the electrolyte is 2-5%; the addition amount of the vinyl sulfate (DTD) is 0.5-1.5%, and if the addition amount of the sulfur-containing high-temperature additive is too small or too large, the problem of gas generation of the battery under high-temperature storage cannot be sufficiently inhibited, residual gas expansion of the battery storage can be caused, and potential safety hazards exist; further, the electrolyte is defined by lithium salt LiPO 2 F 2 、LiPF 6 And the addition amount of LiFSI, if the addition amount of lithium salt is too small or too large, the high-rate startability of the battery may be degraded.
Specifically, in the step a, before the positive electrode slurry is coated on the surface of the aluminum foil, the method further includes a step of batching the positive electrode slurry, and the step of batching the positive electrode slurry includes:
according to the raw material formula, uniformly mixing a binder and a solvent according to the solid content of 7-10% to prepare a positive binder glue solution, and uniformly mixing conductive carbon black, super conductive carbon black and the solvent according to the solid content of 5-10% to prepare a positive conductive agent slurry; and mixing the positive adhesive glue solution and the positive conductive agent slurry for 100-150 min under vacuum, and then adding the NCM ternary material to prepare the positive slurry.
Specifically, in the step of preparing the anode slurry, an NMP (N-methyl pyrrolidone) solvent is used as the solvent, the solid content of the anode binder glue solution is 7-10%, and the dispersion time and effect of the binder can be influenced by the excessively low or high solid content of the anode binder glue solution; the solid content of the anode conductive agent slurry is 5-10%, and the dispersion time and the dispersion effect of the conductive agent can be influenced by too low or too high solid content of the anode conductive agent slurry. The positive electrode slurry prepared by the step of preparing the positive electrode slurry has good stability (the solid content is 58-62%, the viscosity is 9000-12000 mPa & S), the slurry is uniformly dispersed, the coating effect and the appearance consistency are good, the pole piece does not fall off after being coated and rolled by adopting 10-16 mu M aluminum foil, and the adhesion force exceeds 150N/M; the prepared positive electrode slurry has the solid content of 58-62%, the viscosity of 9000-12000 mPa & S and the best coating effect, and when the solid content and the viscosity of the positive electrode slurry are low, the slurry leaks in the coating process, the coating appearance is poor and the weight is unstable; when the solid content of the positive electrode slurry is high and the viscosity is high, the coating appearance is poor and the weight is unstable.
Further, after the positive electrode slurry is prepared, the method further comprises the step of sieving the positive electrode slurry by using a 200-mesh sieve to filter out larger solid particles in the slurry, so that the subsequent coating is prevented from being influenced.
Preferably, in the step a, the aluminum foil has a thickness of 10 to 16 μm.
The thickness of the aluminum foil is limited to be 10-16 mu m, if the thickness of the aluminum foil is too thin, a strip is easy to break during coating, and if the thickness of the aluminum foil is too thick, the cost is high, burrs are easy to be formed after die cutting, and the preparation effect of the positive pole piece is influenced.
Preferably, in the step a, the surface density of the aluminum foil coated with the positive electrode slurry is 120 to 160mg/mm 2 。
The surface density of the aluminum foil coated with the positive electrode slurry is limited, and if the surface density of the aluminum foil coated with the positive electrode slurry is too low, the number of layers is increased, and the lamination efficiency is affected, and if the surface density of the aluminum foil coated with the positive electrode slurry is too high, the starting performance of the battery is poor.
Specifically, in the step B, before the negative electrode slurry is coated on the surface of the copper foil, a step of blending the negative electrode slurry is further included, and the step of blending the negative electrode slurry includes:
uniformly mixing carboxymethyl cellulose and deionized water according to a raw material formula and a solid content of 1-2% to prepare a cathode binder glue solution, and uniformly mixing a conductive agent and the deionized water according to a solid content of 40-45% to prepare a cathode conductive agent slurry; mixing the cathode binder glue solution and the cathode conductive agent slurry under vacuum for 100-150 min, adding artificial graphite, uniformly mixing, adding the styrene butadiene rubber glue solution, and uniformly mixing to obtain the cathode slurry.
Specifically, in the step of batching the negative electrode slurry, the solid content of the negative electrode binder glue solution is 1-2%, and the dispersion time and effect of the binder can be influenced by the excessively low or high solid content of the negative electrode binder glue solution; the solid content of the negative electrode conductive agent slurry is 40-45%, and the dispersion time and effect of the conductive agent can be influenced by too low or too high solid content of the negative electrode conductive agent slurry. The negative electrode slurry prepared by the step of preparing the negative electrode slurry has good stability (the solid content is 42-44%, the viscosity is 2000-4000 mPa.S), the slurry is uniformly dispersed, the coating effect and the appearance consistency are good, a pole piece does not fall off after being rolled by a copper foil with the thickness of 6-8 mu M, and the adhesive force exceeds 20N/M; the prepared negative electrode slurry has the solid content of 42-44%, the viscosity of 2000-4000 mPa.S, and the best coating effect, and when the solid content and the viscosity of the negative electrode slurry are too low, the capacity of the negative electrode slurry leaks in the coating process, the coating appearance is poor, and the weight is unstable; when the solid content and viscosity of the negative electrode slurry are too high, the coating appearance is poor and the weight is unstable.
Further, after the negative electrode slurry is prepared, the negative electrode slurry is sieved by a 200-mesh screen to filter out larger solid particles in the slurry, so that the subsequent coating is prevented from being influenced.
Preferably, in the step B, the copper foil has a thickness of 6 to 8 μm.
The thickness of the copper foil is limited to 6 to 8 μm, and if the thickness of the copper foil is too thin, the coating is easily broken, and if the thickness of the copper foil is too thick, the manufacturing cost of the battery is increased.
In addition, in the lithium ion storage battery with the high-temperature storage resistant emergency starting power supply, the capacity excess ratio of the negative electrode to the positive electrode is 1.08-1.20.
In the high-temperature storage-resistant emergency starting power supply lithium ion storage battery, the capacity excess ratio of the negative electrode to the positive electrode is 1.08-1.20, when the capacity excess ratio of the negative electrode to the positive electrode is too low, the negative electrode separates lithium in the charging and discharging process, potential safety hazards are easy to appear, and when the capacity excess ratio of the negative electrode to the positive electrode is too high, the high-temperature storage-resistant emergency starting power supply lithium ion storage battery is high in cost.
In step C, the positive electrode plate, the negative electrode plate and the diaphragm are combined in a lamination manner, and are baked after being packaged by an aluminum plastic film, and then the electrolyte is injected into the battery cell, and the battery cell is subjected to formation, air exhaust, sealing and capacity grading in sequence to obtain the high-temperature storage emergency starting power supply lithium ion storage battery.
The high-temperature storage resistant emergency starting power supply lithium ion storage battery is prepared by the preparation method of the high-temperature storage resistant emergency starting power supply lithium ion storage battery.
The technical solution of the present invention is further described below by way of specific embodiments.
In order to facilitate an understanding of the present invention, a more complete description of the present invention is provided below. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Comparative example (conventional Battery)
A preparation method of an emergency starting power supply lithium ion storage battery comprises the following steps (a 4000mAh high-temperature-resistant conductive emergency starting lithium ion storage battery is manufactured according to a 7084 type battery):
step A, coating the positive electrode slurry on the surface of an aluminum foil with the thickness of 12 mu m, wherein the surface density of the aluminum foil coated with the positive electrode slurry is 130mg/mm 2 Rolling and die cutting to obtain positive pole pieceCalculating that the raw materials of the positive electrode slurry comprise 95% of NCM ternary material (NCM multi-component material is 523 systems of nickel cobalt lithium manganate), 3% of conductive carbon black and 2% of binder (the binder is specifically PVDF binder);
before coating the anode slurry on the surface of the aluminum foil, the method also comprises a step of batching the anode slurry, wherein the step of batching the anode slurry comprises the following steps: according to the raw material formula, uniformly mixing a binder and a solvent according to the solid content of 7-10% to prepare a positive binder glue solution, and uniformly mixing conductive carbon black and the solvent according to the solid content of 5-10% to prepare a positive conductive agent slurry; mixing the positive adhesive glue solution and the positive conductive agent slurry under vacuum for 120min, and then adding an NCM ternary material to prepare a positive slurry;
b, coating the negative electrode slurry on the surface of copper foil with the thickness of 6 mu m, rolling and die-cutting to obtain a negative electrode plate, wherein the raw materials of the negative electrode slurry comprise 92% of artificial graphite, 4% of conductive agent (conductive agent is conductive carbon black SUPER P Li), 2% of carboxymethyl cellulose and 2% of butadiene styrene rubber glue solution according to weight percentage;
before the negative electrode slurry is coated on the surface of the copper foil, the method also comprises a negative electrode slurry batching step, wherein the negative electrode slurry batching step comprises the following steps: uniformly mixing carboxymethyl cellulose and deionized water according to a raw material formula, wherein the solid content of the carboxymethyl cellulose is 1-2%, so as to prepare a negative electrode binder glue solution, and uniformly mixing a conductive agent and the deionized water according to the solid content of 40-45%, so as to prepare a negative electrode conductive agent slurry; mixing the cathode binder glue solution and the cathode conductive agent slurry for 120min under vacuum, adding artificial graphite, mixing uniformly, adding the styrene butadiene rubber glue solution, and mixing uniformly to obtain cathode slurry;
step C, combining the positive pole piece, the negative pole piece and the diaphragm in a lamination mode, encapsulating, injecting electrolyte into the battery cell, and sequentially carrying out formation, sealing and capacity grading to obtain the lithium ion storage battery with the emergency starting power supply;
the electrolyte is prepared by mixing Ethylene Carbonate (EC), ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) according to the mass ratio of 1C) 0.5%, vinyl sulfate (DTD) 0.5%, liPO 2 F 2 0.3％、LiPF 6 0.6% and LiFSI0.8%.
Example one
A preparation method of a lithium ion storage battery with a high-temperature-resistant storage emergency starting power supply comprises the following steps (4000 mAh high-temperature-resistant conductive emergency starting lithium ion storage battery is manufactured according to a 7084 type battery):
step A, coating the positive electrode slurry on the surface of an aluminum foil with the thickness of 12 mu m, wherein the surface density of the aluminum foil coated with the positive electrode slurry is 130mg/mm 2 The positive pole piece is prepared after rolling and die cutting, the adhesion of the positive pole piece is 232N/M, and the raw materials of the positive pole slurry comprise 91% of NCM ternary material (NCM multi-component material is 523-system nickel cobalt lithium manganate), 3% of conductive carbon black, 3% of super conductive carbon black and 3% of binder (the binder is PVDF binder specifically);
before the anode slurry is coated on the surface of the aluminum foil, the method also comprises the step of batching the anode slurry, wherein the step of batching the anode slurry comprises the following steps: according to the raw material formula, uniformly mixing a binder and a solvent according to the solid content of 7-10% to prepare a positive binder glue solution, and uniformly mixing conductive carbon black, super conductive carbon black and the solvent according to the solid content of 5-10% to prepare a positive conductive agent slurry; mixing the positive adhesive glue solution and the positive conductive agent slurry for 120min under vacuum, and then adding an NCM ternary material to prepare a positive slurry, wherein the solid content of the positive slurry is 58%, and the viscosity of the positive slurry is 11576mPa & S;
b, coating the negative electrode slurry on the surface of a copper foil with the thickness of 6 microns, rolling and die cutting to obtain a negative electrode plate, wherein the adhesion of the negative electrode plate is 29N/M, and the raw materials of the negative electrode slurry comprise 92% of artificial graphite, 4% of conductive agent (conductive agent is conductive carbon black SUPER P Li), 2% of carboxymethyl cellulose and 2% of styrene butadiene rubber glue solution according to weight percentage;
before the negative electrode slurry is coated on the surface of the copper foil, the method also comprises a negative electrode slurry batching step, wherein the negative electrode slurry batching step comprises the following steps: uniformly mixing carboxymethyl cellulose and deionized water according to a raw material formula and a solid content of 1-2% to prepare a cathode binder glue solution, and uniformly mixing a conductive agent and the deionized water according to a solid content of 40-45% to prepare a cathode conductive agent slurry; mixing the negative binder glue solution and the negative conductive agent slurry for 120min under vacuum, adding artificial graphite, uniformly mixing, adding the styrene butadiene rubber glue solution, and uniformly mixing to obtain a negative slurry, wherein the solid content of the negative slurry is 42%, and the viscosity of the negative slurry is 2312mPa & S;
the N/P ratio of the capacities of the anode and the cathode is 1.12;
step C, combining the positive pole piece, the negative pole piece and the diaphragm in a lamination mode, encapsulating, injecting electrolyte into the battery cell, and sequentially carrying out formation, sealing and capacity grading to obtain the high-temperature storage resistant emergency starting power supply lithium ion storage battery;
the electrolyte is obtained by mixing ethylene carbonate and ethyl methyl carbonate according to the mass ratio of 3 2 F 2 0.3％、LiPF 6 0.8% and LiFSI0.8%.
After the battery is manufactured, the conventional battery is tested according to the first embodiment:
(1) the lithium ion storage battery is assembled according to 3 strings and 1 parallel (3S 1P) after 180C discharging for 3S (detected by using a 2000A large-current microcomputer control multifunctional detector), 1C is fully charged under the constant voltage of 12.6V/pack, 180C discharges for 3S, the discharge voltage is greater than 6V/pack, and the test result is shown in figure 1;
(2) 48H is stored at the high temperature of 80 ℃ (detected by using a Guangdong bell BTG-100-D2 constant temperature and humidity box), the lithium ion storage battery is assembled according to 3 strings and 1 parallel (3S 1P), 1C is fully charged under the constant pressure of 12.6V/pack, then 48H is stored at the high temperature of 80 +/-2 ℃, the thickness change rate is 8.50% (less than the standard 10%), the high-temperature storage thickness change rate is far lower than that of a conventional battery before improvement, and the test result is shown in figure 2;
(3) the high-temperature storage battery is stored for 30 days at 65 ℃ (detected by using a Guangdong bell BTG-100-D2 constant-temperature and constant-humidity box), the ion storage battery is assembled according to 3 strings and 1 parallel (3S 1P), 1C is fully charged under the constant pressure of 12.6V/pack, then the storage battery is stored for 30 days at the high temperature of 65 +/-2 ℃, the thickness change rate is 8.24% (less than the standard 10%), the high-temperature storage thickness change rate is far lower than that of a conventional battery before improvement, and the test result is shown in figure 3.
Example two
A preparation method of a lithium ion storage battery with a high-temperature-resistant storage emergency starting power supply comprises the following steps (4000 mAh high-temperature-resistant conductive emergency starting lithium ion storage battery is manufactured according to a 7084 type battery):
step A, coating the positive electrode slurry on the surface of an aluminum foil with the thickness of 12 mu m, wherein the surface density of the aluminum foil coated with the positive electrode slurry is 130mg/mm 2 The positive pole piece is prepared by rolling and die cutting, the adhesion of the positive pole piece is 255N/M, and the raw materials of the positive pole slurry comprise 94% of NCM ternary material (NCM multicomponent material is 523 system nickel cobalt lithium manganate), 1.5% of conductive carbon black, 1.5% of super conductive carbon black and 3% of binder (the binder is PVDF binder specifically);
before the anode slurry is coated on the surface of the aluminum foil, the method also comprises the step of batching the anode slurry, wherein the step of batching the anode slurry comprises the following steps: according to the raw material formula, uniformly mixing a binder and a solvent according to the solid content of 7-10% to prepare a positive binder glue solution, and uniformly mixing conductive carbon black, super conductive carbon black and the solvent according to the solid content of 5-10% to prepare a positive conductive agent slurry; mixing the positive adhesive glue solution and the positive conductive agent slurry for 120min under vacuum, and then adding an NCM ternary material to prepare positive slurry, wherein the solid content of the positive slurry is 61%, and the viscosity of the positive slurry is 10325mPa & S;
step B, coating the negative electrode slurry on the surface of copper foil with the thickness of 6 microns, and rolling and die cutting to obtain a negative electrode plate, wherein the adhesion of the negative electrode plate is 23N/M, and the raw materials of the negative electrode slurry comprise 95% of artificial graphite, 2% of a conductive agent (the conductive agent is conductive carbon black SUPER P Li), 1.5% of carboxymethyl cellulose and 1.5% of styrene butadiene rubber glue solution according to weight percentage;
before the negative electrode slurry is coated on the surface of the copper foil, the method also comprises a negative electrode slurry batching step, wherein the negative electrode slurry batching step comprises the following steps: uniformly mixing carboxymethyl cellulose and deionized water according to a raw material formula and a solid content of 1-2% to prepare a cathode binder glue solution, and uniformly mixing a conductive agent and the deionized water according to a solid content of 40-45% to prepare a cathode conductive agent slurry; mixing the negative binder glue solution and the negative conductive agent slurry for 120min under vacuum, adding artificial graphite, uniformly mixing, adding the styrene butadiene rubber glue solution, and uniformly mixing to obtain a negative slurry, wherein the solid content of the negative slurry is 42%, and the viscosity of the negative slurry is 2633mPa & S;
the capacity N/P ratio of the anode and the cathode is 1.12;
step C, combining the positive pole piece, the negative pole piece and the diaphragm in a lamination mode, encapsulating, injecting electrolyte into the battery cell, and sequentially carrying out formation, sealing and capacity grading to obtain the high-temperature storage resistant emergency starting power supply lithium ion storage battery;
the electrolyte is obtained by mixing ethylene carbonate and ethyl methyl carbonate according to the mass ratio of 3 2 F 2 0.3％、LiPF 6 0.8% and LiFSI0.8%.
After the battery fabrication was completed, the conventional battery was tested as in example two:
(1) 180C discharge 3S (using 2000A heavy current microcomputer to control the multifunctional detector for detection), assembling the lithium ion storage battery according to 3 strings of 1 parallel (3S 1P), fully charging 1C under the constant voltage of 12.6V/pack, 180C discharge 3S, the discharge voltage is more than 6V/pack, and the test result is shown in figure 4;
(2) 48H is stored at the high temperature of 80 ℃ (detected by using a Guangdong bell BTG-100-D2 constant temperature and humidity box), the lithium ion storage battery is assembled according to 3 strings and 1 parallel (3S 1P), 1C is fully charged under the constant pressure of 12.6V/pack, then 48H is stored at the high temperature of 80 +/-2 ℃, the thickness change rate is 8.72% (less than the standard 10%), the high-temperature storage thickness change rate is far lower than that of a conventional battery before improvement, and the test result is shown in figure 5;
(3) the ion storage battery is stored at the high temperature of 65 ℃ for 30 days (detected by using a Guangdong Bell BTG-100-D2 constant temperature and humidity box), the ion storage battery is assembled according to 3 strings and 1 parallel (3S 1P), the 1C is fully charged under the constant pressure of 12.6V/pack, then the ion storage battery is stored at the high temperature of 65 +/-2 ℃ for 30 days, the thickness change rate is 8.92 percent (less than 10 percent of the standard), the high-temperature storage thickness change rate is far lower than that of a conventional battery before improvement, and the test result is shown in figure 6.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of a high-temperature storage resistant lithium ion storage battery with an emergency starting power supply is characterized by comprising the following steps:
step A, coating anode slurry on the surface of an aluminum foil, rolling and die-cutting to obtain an anode plate, wherein the anode slurry comprises, by weight, 91-94% of an NCM ternary material, 1-3% of conductive carbon black, 1-3% of super conductive carbon black and 2-3% of a binder;
b, coating the negative electrode slurry on the surface of copper foil, rolling and die-cutting to obtain a negative electrode plate, wherein the raw materials of the negative electrode slurry comprise 92-95% of artificial graphite, 2-4% of a conductive agent, 1-2% of carboxymethyl cellulose and 1-2% of styrene-butadiene rubber glue solution according to weight percentage;
step C, combining the positive pole piece, the negative pole piece and the diaphragm in a lamination mode, injecting electrolyte into the battery cell after packaging, and preparing the high-temperature storage-resistant emergency starting power supply lithium ion storage battery after formation, sealing and capacity grading in sequence;
the electrolyte is obtained by mixing ethylene carbonate and ethyl methyl carbonate, and a sulfur-containing high-temperature additive and a lithium salt are added into the electrolyte.
2. The method for preparing a lithium ion battery with high temperature storage resistance and emergency starting power supply according to claim 1, wherein in the step C, the electrolyte is prepared by mixing ethylene carbonate and ethyl methyl carbonate according to a mass ratio of 3 2 F 2 、LiPF 6 And LiFSI.
3. The method for preparing a lithium ion battery with emergency starting power supply and high temperature storage resistance according to claim 2, wherein the electrolyte is added with 2-5% of 1, 3-propane sultone, 0.5-1.5% of vinyl sulfate and LiPO according to the percentage of the total weight of the electrolyte 2 F 2 0.2～0.5％、LiPF 6 0.5 to 1.0 percent and LiFSI0.5 to 1.0 percent.
4. The method for preparing a lithium ion battery with high temperature storage resistance and emergency starting power supply according to claim 1, wherein in the step A, before the positive electrode slurry is coated on the surface of the aluminum foil, the method further comprises a step of preparing the positive electrode slurry, and the step of preparing the positive electrode slurry comprises the following steps:
according to the raw material formula, uniformly mixing a binder and a solvent according to the solid content of 7-10% to prepare a positive binder glue solution, and uniformly mixing conductive carbon black, super conductive carbon black and the solvent according to the solid content of 5-10% to prepare a positive conductive agent slurry; and mixing the positive adhesive glue solution and the positive conductive agent slurry for 100-150 min under vacuum, and then adding the NCM ternary material to prepare the positive slurry.
5. The method for preparing a lithium ion battery with emergency starting power supply for high temperature storage according to claim 1, wherein in the step A, the thickness of the aluminum foil is 10-16 μm.
6. The method of claim 1The preparation method of the high-temperature storage resistant lithium ion storage battery with the emergency starting power supply is characterized in that in the step A, the surface density of the aluminum foil surface coated with the anode slurry is 120-160 mg/mm 2 。
7. The method for preparing the lithium ion battery with the emergency starting power supply and the high-temperature storage resistance according to claim 1, wherein in the step B, before the negative electrode slurry is coated on the surface of the copper foil, the method further comprises a step of preparing the negative electrode slurry, and the step of preparing the negative electrode slurry comprises the following steps of:
uniformly mixing carboxymethyl cellulose and deionized water according to a raw material formula and a solid content of 1-2% to prepare a cathode binder glue solution, and uniformly mixing a conductive agent and the deionized water according to a solid content of 40-45% to prepare a cathode conductive agent slurry; mixing the cathode binder glue solution and the cathode conductive agent slurry under vacuum for 100-150 min, adding artificial graphite, uniformly mixing, adding the styrene butadiene rubber glue solution, and uniformly mixing to obtain the cathode slurry.
8. The method for preparing a lithium ion battery with high temperature storage resistance and emergency starting power supply according to claim 1, wherein in the step B, the thickness of the copper foil is 6-8 μm.
9. The method for preparing the lithium ion battery with the emergency starting power supply and the high-temperature storage resistance according to claim 1, wherein the capacity excess ratio of the negative electrode to the positive electrode in the lithium ion battery with the emergency starting power supply and the high-temperature storage resistance is 1.08-1.20.
10. The lithium ion storage battery with the high-temperature storage resistance and the emergency starting power supply is prepared by the preparation method of the lithium ion storage battery with the high-temperature storage resistance and the emergency starting power supply according to any one of claims 1 to 9.
CN202211042916.4A 2022-08-29 2022-08-29 High-temperature-resistant storage lithium ion storage battery with emergency starting power supply and preparation method thereof Pending CN115275371A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117477039A (en) * 2023-12-19 2024-01-30 宁德新能源科技有限公司 Secondary battery and electronic device including the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117477039A (en) * 2023-12-19 2024-01-30 宁德新能源科技有限公司 Secondary battery and electronic device including the same

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