CN110311138B - Lithium ion secondary battery with thermal protection function - Google Patents
Lithium ion secondary battery with thermal protection function Download PDFInfo
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- CN110311138B CN110311138B CN201910622969.5A CN201910622969A CN110311138B CN 110311138 B CN110311138 B CN 110311138B CN 201910622969 A CN201910622969 A CN 201910622969A CN 110311138 B CN110311138 B CN 110311138B
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
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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
- H01M10/42—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
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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
- 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
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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
- H01M2200/00—Safety devices for primary or secondary batteries
- H01M2200/10—Temperature sensitive devices
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a lithium ion secondary battery with a thermal motion protection function, which consists of a positive pole piece, a negative pole piece, a diaphragm, electrolyte, a shell and an electrode leading-out end, and contains two thermal motion protection materials, wherein the thermal motion protection material A is a polymer or oligomer of bismaleimide and barbituric acid, is added into the positive pole piece, and is coated on the surface of a positive active substance or distributed around the positive active substance; the thermal action protective material B is bismaleimide micromolecule and is dissolved in the electrolyte; the thermal operating temperature is 90-200 ℃, when the temperature of the whole or part of the battery is raised to the thermal operating temperature, the material B in the electrolyte rapidly migrates and gathers to the material A for reaction to form a cross-linked polymer, and the positive active substance and the electrolyte are isolated, so that the thermal runaway of the battery is prevented. Compared with the prior solution, the invention can more effectively inhibit the occurrence of thermal runaway, improve the safety of the battery and simultaneously reduce the influence of the battery on other performances.
Description
Technical Field
The invention relates to the technical field of lithium ion secondary batteries, in particular to a lithium ion secondary battery with a thermal driving protection function.
Background
Lithium ion secondary batteries have the advantages of high voltage, high energy density and the like, are widely applied to power supplies of consumer electronics, energy storage systems and power systems, and the safety and environmental reliability of lithium ion batteries are the most concerned problems in the industry and the academia all the time. Lithium ion battery can lead to inside heat accumulation because of overcurrent, inside dendrite leads to abuse conditions such as internal short circuit or overcharge, when the heat accumulation reaches certain degree, can cause electrolyte, anodal and inside other materials to take place exothermic chain reaction, finally leads to the lithium cell to take place the thermal runaway.
Research shows that for lithium ion secondary batteries with positive electrode materials of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium manganate and lithium nickel cobalt aluminate, the reaction of the positive electrode material and an electrolyte is a main reason for triggering thermal runaway. Therefore, many researches have been made to invent a method of thermal-mechanical protection, so as to timely block the contact between the cathode material and the electrolyte before the cathode material reacts with the electrolyte, thereby preventing the occurrence of thermal runaway.
Bismaleimide-like materials have been one of the hot candidates for thermal dynamic protection schemes with the advantages: the polymer is soluble in electrolyte, has high polymerization reaction speed, and the polymerized product is high-temperature resistant, non-combustible and non-conductive. The bismaleimide monomer is relatively stable, self-polymerization is difficult to occur under the condition without an initiator, and thermal polymerization can be realized only by the initiator or an active site, so that the purpose of thermal action protection is achieved.
The existing technical scheme comprises: for example, patent application No. 201710428782.2 discloses that bismaleimide monomer or oligomer and polymerization initiator such as azobisisobutyronitrile are mixed and added into electrolyte, and the initiator initiates polymerization of bismaleimide monomer under heating. The scheme has the defects that azodiisobutyronitrile and other classical common initiators are relatively active, partial reaction occurs at a low temperature of 60-80 ℃, gas generation or self-polymerization occurs during high-temperature storage and high-temperature circulation, and normal high-temperature use of the battery is influenced; meanwhile, the polymer is polymerized in the electrolyte and can not be oriented to separate the electrolyte from electrode active substances.
In some cases, such as when barbituric acids are used as initiators, bismaleimide polymerization results in highly branched polymers and self-terminates due to steric effects, thereby preserving many active sites. The invention patent with the patent application number of 200910151296.6 utilizes the hyperbranched polymers to be added into a positive pole piece to coat a positive active material to form a thermal action protective film. When heated, the active sites of the hyperbranched polymer continue to react with each other, isolating the positive active material and the electrolyte. The disadvantages of this solution are: the high-branched polymer has a large molecular weight and cannot move in an electrode, the distance of the residual active sites on the branched chain is long, and a large amount of polymer needs to be added to carry out thicker and compact coating on the surface of the positive electrode if the high-branched polymer is required to react, and the thicker and compact coating can increase the internal resistance of the battery and further influence the performances of rate discharge, low-temperature discharge and the like of the battery.
The invention patent with application number 201110461184.8 applies the highly branched oligomer of bismaleimide to the electrolyte, and has the following disadvantages: the oligomer with a large molecular weight can obviously increase the viscosity of the electrolyte, and can not smoothly migrate in the electrolyte, thereby increasing the internal resistance of the battery and further influencing the performance of the battery such as rate discharge, low-temperature discharge and the like.
Disclosure of Invention
The invention aims to: provided is a lithium ion battery having a thermal driving protection function, which actively isolates contact between an electrode active material and an electrolyte before a thermal runaway temperature when an abnormal safety problem occurs in the battery, thereby preventing the occurrence of thermal runaway and safety accidents.
The invention provides a lithium ion secondary battery with a thermal dynamic protection function, wherein the thermal dynamic protection adopts a double-protection synergistic mode, the battery consists of a positive pole piece, a negative pole piece, a diaphragm, electrolyte, a shell and an electrode leading-out end, and contains two thermal dynamic protection materials, the thermal dynamic protection material A is a polymer or oligomer formed by bismaleimide shown in a chemical formula (I) and/or a chemical formula (II) and barbituric acid shown in a chemical formula (III), the average molecular weight of the polymer or oligomer is 10000-1000000, and the polymer or oligomer is added into the electrode piece; the thermal action protective material B is a bismaleimide micromolecule shown in a chemical formula (I) and/or a chemical formula (II), has an average molecular weight of less than 2000, and is dissolved in the electrolyte.
Thermoacting protective materials A and B, wherein R3Selected from-R-, -RNH2R-、-C(O)CH2-、-CH2OCH2-、-C(O)-、 -O-、-O-O-、-S-、-S-S-、-S(O)-、-CH2S(O)CH2-、-(O)S(O)-、-C6H5-、-CH2(C6H5)CH2-、 -CH2(C6H5) One of (O) -, phenylene and biphenylene; r6Selected from the group consisting of-R-, -C (O) -, -C (CH)3)2-、-O-C6H5-C(CH3)2-C6H5One of-O-, -O-O-, -S-S-, -S (O) -, - (O) S (O) -; wherein R is1、R2、R4And R5Each independently selected from H, F, R or-O-R; and R is C1-6 alkyl or fluorinated alkyl.
The average molecular weight of the thermal acting protective material A is preferably 10000-300000.
Wherein R is7And R8Each independently selected from H, F, R9And R10Each independently selected from H, F, R or-O-R; and R is C1-6 alkyl or fluorinated alkyl.
The weight ratio of the electrode plate containing the thermal action protection material A is 0.01-2%.
The electrolyte contains 0.01-5 wt% of the thermal action protective material B.
For the lithium ion battery containing one or more of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium manganate and lithium nickel cobalt aluminate in the positive pole piece, the thermal acting protective material A is added in the positive pole piece.
The preparation process of the positive pole piece comprises the following steps: 1) dissolving the thermal acting protective material A in N-methyl pyrrolidone or other organic solvents; 2) mixing and stirring the solution of the thermal acting protective material A and the positive active substance; 3) adding other auxiliary materials such as conductive agent, adhesive, solvent and the like, stirring and pulping; 4) and coating the slurry on the surface of the foil and drying to prepare the pole piece. The thermal action protective material A is required to be mixed with the positive active substance firstly, and then the conductive agent and the adhesive are added, so that the thermal action protective material A is coated on the surface of the positive active substance, but not on the surfaces of the conductive agent and the adhesive, and a better effect can be achieved.
The preparation process of the thermal acting protective material A comprises the following steps: 1) dissolving a bismaleimide monomer with a chemical general formula (I) and/or (II) into a proper solvent to form a solution C; 2) dissolving a barbituric acid monomer with a chemical general formula (III) into a proper solvent to form a solution D; 3) mixing the solution C and the solution D according to a certain proportion to ensure that the molar ratio of the bismaleimide monomer with the chemical general formula (I) and/or (II) to the barbituric acid monomer with the chemical general formula (III) is 10-0.1: 1, heating to 90-200 ℃, and carrying out heat preservation reaction for 30 minutes to 8 hours; 4) adding phase separation solution to precipitate the product, centrifuging or filtering for separation, and drying to obtain thermal motion protective material A.
Fig. 1 is a schematic diagram illustrating the operation of the present invention, wherein a thermo-kinetic protective material a provides active sites as "anchor points" in the vicinity of the active material, and since a thermo-kinetic protective material B is a small molecule, it can move freely in the electrolyte. When the battery is used conventionally, the addition amount of A is not required to be too much, and B is small molecule, so that the viscosity of the electrolyte is not greatly increased, and the conventional electrical property is not obviously influenced. When local safety problems (such as acupuncture, local short circuit and the like) are met, the small molecules of the B can rapidly move to the surface position of the active substance in a local overheating area, and are rapidly polymerized and crosslinked at the active site of the A, so that the electrolyte and the active substance are isolated, and thermal runaway is prevented. A. The two thermal action protective materials B have synergistic effect, and the safety performance of the battery cell is greatly improved on the basis of not influencing the conventional performance.
Drawings
Fig. 1 is a schematic diagram of the principle of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Description of the synthesis of the thermal protective Material A:
table 1 lists the chemical formulae of the raw materials used in the examples.
Step 1: dissolving a bismaleimide monomer with a chemical formula B in the following table into a proper solvent to form a solution C, wherein the solvent can be N-methyl pyrrolidone, gamma-butyrolactone, N, N-dimethylformamide, diethyl carbonate, ethylene carbonate, propylene carbonate and the like;
step 2: dissolving a barbituric acid monomer with a chemical formula of E in the following table into a proper solvent to form a solution D, wherein the solvent can be N-methyl pyrrolidone, gamma-butyrolactone, N, N-dimethylformamide, diethyl carbonate, ethylene carbonate, propylene carbonate and the like;
and step 3: mixing and heating the solution C and the solution D in a certain proportion to 90-200 ℃, and carrying out heat preservation reaction for 30 minutes to 8 hours;
and 4, step 4: adding phase separation solution such as methanol, ethanol, propanol or water, precipitating, centrifuging or filtering, and drying to obtain thermal action protective material A.
Table 1 chemical formulae of raw materials used in examples.
Example 1
Step 1: dissolving a bismaleimide monomer with a chemical formula of B1 into N-methyl pyrrolidone to form a solution C1, wherein the concentration of C1 is 5 mol/L;
step 2: dissolving a barbituric acid monomer with a chemical formula of E1 into N-methyl pyrrolidone to form a solution D1, wherein the concentration of D1 is 5 mol/L;
and step 3: mixing the solution C1 and the solution D1 in a volume ratio of 2:1, heating to 130 ℃, and keeping the temperature to react for 1 hour;
and 4, step 4: adding ethanol with the volume being three times of that of the solution to precipitate the product, centrifuging or filtering and separating, and drying at 60 ℃ to obtain the thermal motion protective material A1. The molecular weight of A1 was 50000Mw by GPC.
Example 2
Step 1: dissolving a bismaleimide monomer with a chemical formula of B2 into gamma-butyrolactone to form a solution C2, wherein the concentration of C2 is 7 mol/L;
step 2: dissolving a barbituric acid monomer with a chemical formula of E2 into gamma-butyrolactone to form a solution D2, wherein the concentration of D2 is 9 mol/L;
and step 3: mixing the solution C2 and the solution D2 according to the volume ratio of 4:1, heating to 160 ℃, and keeping the temperature to react for 2 hours;
and 4, step 4: adding methanol with the volume being three times that of the solution to precipitate the product, centrifuging or filtering the product, and drying the product at 80 ℃ to obtain the thermal motion protective material A2. The molecular weight of A2 was 150000Mw by GPC.
Example 3
Step 1: dissolving a bismaleimide monomer with a chemical formula of B3 into propylene carbonate to form a solution C3, wherein the concentration of C3 is 2 mol/L;
step 2: dissolving a barbituric acid monomer with a chemical formula of E3 into propylene carbonate to form a solution D3, wherein the concentration of D3 is 3 mol/L;
and step 3: mixing the solution C3 and the solution D3 in a volume ratio of 3:1, heating to 120 ℃, and keeping the temperature to react for 6 hours;
and 4, step 4: adding propanol three times the volume of the solution to precipitate the product, centrifuging or filtering, and drying at 80 ℃ to obtain the thermal motion protective material A3. The molecular weight of A3 was 30000Mw by GPC.
Example 4
Step 1: dissolving a bismaleimide monomer with a chemical formula of B3 into N, N-dimethylformamide to form a solution C4, wherein the concentration of C4 is 8 mol/L;
step 2: dissolving a barbituric acid monomer with a chemical formula of E3 into N, N-dimethylformamide to form a solution D4, wherein the concentration of D4 is 8 mol/L;
and step 3: mixing the solution C4 and the solution D4 in a volume ratio of 1:1, heating to 180 ℃, and keeping the temperature to react for 6 hours;
and 4, step 4: adding water with five times of the volume of the solution to precipitate the product, centrifuging or filtering and separating, and drying at 55 ℃ to obtain the thermal action protective material A4. The molecular weight of A4 was 200000Mw by GPC.
Description of typical cell fabrication:
preparing a positive pole piece: 1) dissolving a thermal acting protective material A in N-methyl pyrrolidone; 2) mixing and stirring the solution of the thermal acting protective material A and a positive active material lithium cobaltate; 3) adding a conductive agent SuperP and a binding agent PVDF, leading the weight ratio of Lithium Cobaltate (LCO), the thermal acting protective material A, PVDF and SuperP to be (96-x) x:2:2, and stirring for pulping; 4) Coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting pieces and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite (or containing silicon, silicon alloy, silicon-carbon composite, silicon oxide, or tin, tin alloy and tin oxide), Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing an electrolyte: and adding a proper amount of the thermal protection material B into the electrolyte, and stirring and dissolving to obtain the electrolyte.
Preparing a lithium ion battery: assembling the negative pole piece, the positive pole piece and the diaphragm which are prepared according to the process to prepare a battery cell, filling the battery cell into an outer package, injecting the electrolyte into the battery cell, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
Description of the test methods:
and (3) high-temperature storage test: fully charging at room temperature according to a standard charging mode, storing in a forced air oven at 85 +/-2 ℃ for 6 hours, immediately testing the thickness after taking out, discharging to 3.0V according to 0.2 ℃ after cooling to room temperature to test the residual capacity, and testing the recovery capacity at room temperature by using a standard charging and discharging mode.
And (3) needle punching test: fully charging at room temperature according to a standard charging mode, and needling the central point position of the sample by using a steel needle with the diameter of 3.0mm and the speed of 100 +/-10 mm/s.
2C discharge rate performance test: fully charged at room temperature according to a standard charging mode, discharged to 3.0V by different 2C currents, and tested for discharge capacity, compared with 0.2C.
Comparative examples and examples of batteries illustrate:
the following comparative examples and examples all adopt a flexible package polymer lithium ion battery with a rated capacity of 3000mAh as an experimental platform.
Comparative example 1:
preparing a positive pole piece: and (2) stirring and pulping Lithium Cobaltate (LCO), PVDF and Super-P at a weight ratio of 96:2:2, coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing a lithium ion battery: assembling the negative pole piece and the positive pole piece prepared by the process with a diaphragm to prepare a battery cell, filling the battery cell into an outer package, injecting conventional electrolyte into the outer package, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
Comparative example 2:
preparing a positive pole piece: 1) dissolving thermal acting protective material A1 in N-methyl pyrrolidone; 2) mixing and stirring the solution of the thermal acting protective material A1 and the positive active material lithium cobaltate; 3) adding a conductive agent SuperP and a binder PVDF to ensure that the weight ratio of Lithium Cobaltate (LCO), a thermal acting protective material A1, PVDF and SuperP is 95.5:0.5:2:2, and stirring for pulping; 4) coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting pieces and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing a lithium ion battery: assembling the negative pole piece, the positive pole piece and the diaphragm which are prepared according to the process to prepare a battery cell, filling the battery cell into an outer package, injecting conventional electrolyte into the battery cell, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
Comparative example 3:
preparing a positive pole piece: 1) dissolving thermal acting protective material A1 in N-methyl pyrrolidone; 2) mixing and stirring the solution of the thermal acting protective material A1 and the positive active material lithium cobaltate; 3) adding a conductive agent SuperP and a binder PVDF to ensure that the weight ratio of Lithium Cobaltate (LCO), a thermal acting protective material A1, PVDF and SuperP is 93:3:2:2, and stirring for pulping; 4) Coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting pieces and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing a lithium ion battery: assembling the negative pole piece and the positive pole piece prepared by the process with a diaphragm to prepare a battery cell, filling the battery cell into an outer package, injecting conventional electrolyte into the outer package, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
Comparative example 4:
preparing a positive pole piece: and (2) stirring and pulping Lithium Cobaltate (LCO), PVDF and Super-P at a weight ratio of 96:2:2, coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing an electrolyte: adding the thermal protection material B1 and the initiator azobisisobutyronitrile according to the weight ratio of 10:1 into the electrolyte, wherein the content of B1 is 5% of the electrolyte, stirring and dissolving to obtain the electrolyte 4.
Preparing a lithium ion battery: and assembling the negative pole piece and the positive pole piece prepared by the process with a diaphragm to prepare a battery cell, filling the battery cell into an outer package, injecting the electrolyte 4 into the outer package, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
Example 1:
preparing a positive pole piece: 1) dissolving thermal acting protective material A1 in N-methyl pyrrolidone; 2) mixing and stirring the solution of the thermal acting protective material A1 and the positive active material lithium cobaltate; 3) adding a conductive agent SuperP and a binder PVDF to ensure that the weight ratio of Lithium Cobaltate (LCO), a thermal acting protective material A1, PVDF and SuperP is 95.5:0.5:2:2, and stirring for pulping; 4) coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting pieces and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing an electrolyte: adding the thermal protection material B1 into the electrolyte, wherein the content of B1 is 5% of the electrolyte, and stirring to dissolve to obtain the electrolyte 5.
Preparing a lithium ion battery: and assembling the negative pole piece and the positive pole piece prepared by the process with a diaphragm to prepare a battery cell, filling the battery cell into an outer package, injecting the electrolyte 5 into the outer package, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
Example 2:
preparing a positive pole piece: 1) dissolving thermal acting protective material A1 in N-methyl pyrrolidone; 2) mixing and stirring the solution of the thermal acting protective material A1 and the positive active material lithium cobaltate; 3) adding a conductive agent SuperP and a binder PVDF, and stirring and pulping Lithium Cobaltate (LCO), a thermal acting protective material A1, PVDF and SuperP in a weight ratio of 95:1:2: 2; 4) Coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting pieces and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing an electrolyte: adding the thermal protection material B1 into the electrolyte, wherein the content of B1 is 2% of the electrolyte, and stirring to dissolve to obtain the electrolyte 6.
Preparing a lithium ion battery: and assembling the negative pole piece and the positive pole piece prepared by the process with a diaphragm to prepare a battery cell, filling the battery cell into an outer package, injecting the electrolyte 6 into the outer package, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
Example 3:
preparing a positive pole piece: 1) dissolving thermal acting protective material A1 in N-methyl pyrrolidone; 2) mixing and stirring the solution of the thermal acting protective material A1 and the positive active material lithium cobaltate; 3) adding a conductive agent SuperP and a binder PVDF to ensure that the weight ratio of Lithium Cobaltate (LCO), a thermal acting protective material A1, PVDF and SuperP is 95.7:0.3:2:2, and stirring to prepare pulp; 4) coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting pieces and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing an electrolyte: the thermal protective material B1 was added to the electrolyte solution to a content of B1 of 4% of the electrolyte solution, and dissolved by stirring to obtain an electrolyte solution 7.
Preparing a lithium ion battery: and assembling the negative pole piece and the positive pole piece prepared by the process with a diaphragm to prepare a battery cell, filling the battery cell into an outer package, injecting the electrolyte 7 into the outer package, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
Example 4:
preparing a positive pole piece: 1) dissolving thermal acting protective material A2 in N-methyl pyrrolidone; 2) mixing and stirring the solution of the thermal acting protective material A2 and the positive active material lithium cobaltate; 3) adding a conductive agent SuperP and a binder PVDF to ensure that the weight ratio of Lithium Cobaltate (LCO), a thermal acting protective material A2, PVDF and SuperP is 94.5:1.5:2:2, and stirring for pulping; 4) coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting pieces and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing an electrolyte: adding the thermal protection material B2 into the electrolyte, wherein the content of B2 is 0.5 percent of the electrolyte, stirring and dissolving to prepare the electrolyte 8.
Preparing a lithium ion battery: and assembling the negative pole piece and the positive pole piece prepared by the process with a diaphragm to prepare a battery cell, filling the battery cell into an outer package, injecting the electrolyte 8 into the outer package, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
Example 5:
preparing a positive pole piece: 1) dissolving thermal acting protective material A3 in N-methyl pyrrolidone; 2) mixing and stirring the solution of the thermal acting protective material A3 and the positive active material lithium cobaltate; 3) adding a conductive agent SuperP and a binder PVDF to ensure that the weight ratio of Lithium Cobaltate (LCO), a thermal acting protective material A3, PVDF and SuperP is 94.8:1.2:2:2, and stirring for pulping; 4) coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting pieces and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing an electrolyte: adding the thermal protection material B3 into the electrolyte, wherein the content of B3 is 2% of the electrolyte, and stirring to dissolve to obtain the electrolyte 9.
Preparing a lithium ion battery: and assembling the negative pole piece and the positive pole piece prepared by the process with a diaphragm to prepare a battery cell, filling the battery cell into an outer package, injecting the electrolyte 9 into the outer package, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
Example 6:
preparing a positive pole piece: 1) dissolving thermal acting protective material A4 in N-methyl pyrrolidone; 2) mixing and stirring the solution of the thermal acting protective material A4 and the positive active material lithium cobaltate; 3) adding a conductive agent SuperP and a binder PVDF to ensure that the weight ratio of Lithium Cobaltate (LCO), a thermal acting protective material A4, PVDF and SuperP is 95.9:0.1:2:2, and stirring for pulping; 4) coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting pieces and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing an electrolyte: the thermal protection material B4 was added to the electrolyte solution, the content of B4 was 4% of the electrolyte solution, and the electrolyte solution 10 was prepared by stirring and dissolving.
Preparing a lithium ion battery: assembling the negative pole piece, the positive pole piece and the diaphragm which are prepared according to the process to prepare a battery cell, filling the battery cell into an outer package, injecting the electrolyte 10 into the battery cell, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
Example 7:
preparing a positive pole piece: 1) dissolving thermal acting protective material A3 in N-methyl pyrrolidone; 2) mixing and stirring the solution of the thermal acting protective material A3 and the positive active material lithium cobaltate; 3) adding a conductive agent SuperP and a binder PVDF to ensure that the weight ratio of Lithium Cobaltate (LCO), a thermal acting protective material A3, PVDF and SuperP is 95.2:0.8:2:2, and stirring for pulping; 4) coating the two sides of the positive electrode slurry on a positive electrode current collector, and drying, compacting, cutting pieces and welding tabs to obtain the positive electrode piece.
Preparing a negative pole piece: adding artificial graphite, Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC) serving as negative active materials into deionized water according to the required weight ratio of 96:2:2, stirring and homogenizing to prepare negative slurry; coating the two sides of the negative electrode slurry on a negative electrode current collector, and drying, compacting, slitting, cutting and welding tabs to obtain a negative electrode plate.
Preparing an electrolyte: the thermal protective material B1 was added to the electrolyte solution, and the content of B1 was 3.5% of the electrolyte solution, and stirred and dissolved to prepare an electrolyte solution 11.
Preparing a lithium ion battery: and assembling the negative pole piece and the positive pole piece prepared by the process with a diaphragm to prepare a battery cell, filling the battery cell into an outer package, injecting the electrolyte 11 into the outer package, sealing, pre-charging, and forming to prepare the lithium ion secondary battery.
The experimental results are as follows:
and (3) analyzing an experimental result:
compared with the comparative battery example, the battery example has the advantages that the anchor points of the bismaleimide polymer are added into the electrode in a small amount, and the bismaleimide monomer is added into the electrolyte, so that the safety performance can be greatly improved, and the conventional performances such as internal resistance, rate discharge and high-temperature storage can be kept unchanged in a double-protection synergistic mode.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (9)
1. A lithium ion secondary battery with a thermal protection function is composed of a positive pole piece, a negative pole piece, a diaphragm, electrolyte, a shell and an electrode leading-out end, and is characterized in that: the electrode plate comprises two thermal acting protective materials, wherein the thermal acting protective material A is a polymer formed by bismaleimide shown in a chemical formula (I) and/or a chemical formula (II) and barbituric acid shown in a chemical formula (III), the average molecular weight of the polymer is 10000-1000000, and the polymer is added into the electrode plate; the thermal action protection material B is a bismaleimide micromolecule shown in a chemical formula (I) and/or a chemical formula (II), has an average molecular weight of less than 2000, and is dissolved in electrolyte; when the local safety problem is met, the micromolecules of B can rapidly move to the surface position of the active substance in the local overheating area, and the active substance is rapidly polymerized and crosslinked at the active site of A, so that the electrolyte and the active substance are isolated, and the thermal runaway is prevented;
wherein R is3Selected from-R-, -RNH2R-、 -C(O)CH2-、 -CH2OCH2-、 -C(O)-、 -O-、 -O-O-、 -S-、 -S-S-、 -S(O)-、 -CH2S(O)CH2-、 -(O)S(O)-、 -C6H5-、 -CH2(C6H5)CH2-、 -CH2(C6H5) One of (O) -, phenylene and biphenylene; r6Selected from the group consisting of-R-, -C (O) -, -C (CH)3)2-、 -O-C6H5-C(CH3)2-C6H5One of-O-, -O-O-, -S-S-, -S (O) -, - (O) S (O) -; r is1、R2、R4And R5Each independently selected from H, F, R or-O-R; and R is C1-6 alkyl or fluorinated alkyl.
2. The lithium ion secondary battery having a thermal protection function according to claim 1, characterized in that: wherein R is7And R8Each independently selected from H, F, R9And R10Each independently selected from H, F, R or-O-R; and R is C1-6 alkyl or fluorinated alkyl.
3. The lithium ion secondary battery having a thermal protection function according to claim 1, characterized in that: the weight ratio of the electrode plate containing the thermal action protection material A is 0.01-2%.
4. The lithium ion secondary battery having a thermal protection function according to claim 1, characterized in that: the electrolyte contains 0.01-5 wt% of the thermal action protective material B.
5. The lithium ion secondary battery having a thermal protection function according to claim 1, characterized in that: the average molecular weight of the thermal acting protective material A is 10000-300000.
6. The lithium ion secondary battery having a thermal dynamic protection function according to claim 1, wherein: the positive pole piece contains one or more of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium manganate and lithium nickel cobalt aluminate, and the thermal action protective material A is added into the positive pole piece.
7. The lithium ion secondary battery having a thermal protection function according to claim 6, characterized in that: the preparation process of the positive pole piece comprises the following steps: 1) dissolving a thermokinetic protective material A in an organic solvent; 2) mixing and stirring a solution containing a thermal acting protective material A and a positive active substance; 3) adding conductive agent, adhesive, solvent and auxiliary materials, stirring and pulping; 4) and coating the slurry on the surface of the foil and drying to prepare the pole piece.
8. The lithium ion secondary battery having a thermal protection function according to claim 1, characterized in that: the preparation process of the thermal acting protective material A comprises the following steps: 1) dissolving a bismaleimide monomer with a chemical general formula (I) and/or (II) into a proper solvent to form a solution C; 2) dissolving a barbituric acid monomer with a chemical general formula (III) into a proper solvent to form a solution D; 3) mixing the solution C and the solution D according to a certain proportion to ensure that the molar ratio of the bismaleimide monomer with the chemical general formula (I) and/or (II) to the barbituric acid monomer with the chemical general formula (III) is 10-0.1: 1, heating to 90-200 ℃, and carrying out heat preservation reaction for 30 minutes to 8 hours; 4) adding phase separation solution to precipitate the product, centrifuging or filtering for separation, and drying to obtain thermal action protective material A.
9. The lithium ion secondary battery having a thermal protection function according to claim 7, characterized in that: the solvent is N-methyl pyrrolidone, gamma-butyrolactone, N-dimethylformamide, diethyl carbonate, ethylene carbonate or propylene carbonate; the phase separation solution is methanol, ethanol, propanol or water.
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| CN114031778B (en) * | 2021-11-09 | 2023-03-17 | 远景动力技术(江苏)有限公司 | Electrode slurry additive, preparation method thereof, positive electrode and lithium ion battery |
| CN115986056B (en) * | 2023-03-17 | 2023-06-13 | 宁德新能源科技有限公司 | Secondary battery and electronic device |
| CN117239143B (en) * | 2023-10-26 | 2024-02-20 | 广州纳诺新材料科技有限公司 | Self-sealing carbon-coated foil, high-safety battery and preparation method thereof |
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