CN113437352B - Battery and preparation method thereof - Google Patents

Battery and preparation method thereof Download PDF

Info

Publication number
CN113437352B
CN113437352B CN202110704327.7A CN202110704327A CN113437352B CN 113437352 B CN113437352 B CN 113437352B CN 202110704327 A CN202110704327 A CN 202110704327A CN 113437352 B CN113437352 B CN 113437352B
Authority
CN
China
Prior art keywords
electrolyte
battery
flame
retardant electrolyte
plate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110704327.7A
Other languages
Chinese (zh)
Other versions
CN113437352A (en
Inventor
谢孔岩
彭冲
李俊义
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhuhai Cosmx Battery Co Ltd
Original Assignee
Zhuhai Cosmx Battery Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhuhai Cosmx Battery Co Ltd filed Critical Zhuhai Cosmx Battery Co Ltd
Priority to CN202110704327.7A priority Critical patent/CN113437352B/en
Publication of CN113437352A publication Critical patent/CN113437352A/en
Application granted granted Critical
Publication of CN113437352B publication Critical patent/CN113437352B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62C—FIRE-FIGHTING
    • A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
    • A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides a battery and a preparation method of the battery, wherein the battery comprises a shell, a battery core and electrolyte, and the shell accommodates the battery core and the electrolyte; the battery cell comprises a positive plate, wherein a hole is formed in the positive plate; the electrolyte comprises a solid flame-retardant electrolyte, at least part of which is positioned in the pores of the positive plate; wherein the solid state flame retardant electrolyte comprises an X group, X being as follows:
Figure DDA0003131575270000011
the solid flame-retardant electrolyte has certain flexibility, enhances the tensile resistance of the positive plate, improves the heavy-load impact resistance of the positive plate and improves the safety performance of the battery.

Description

Battery and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a battery and a preparation method of the battery.
Background
Since commercialization of lithium ion batteries, the lithium ion batteries are widely used due to the characteristics of high energy density, high power density, good cycle performance, no memory effect, green environmental protection and the like.
Currently, the positive electrode of a lithium ion battery generally includes an aluminum foil and an active material layer, and the negative electrode generally includes a copper foil and graphite. However, the lithium ion battery is easy to cause internal short circuit phenomenon due to contact of the positive aluminum foil and the negative graphite due to heavy impact and the like, and serious safety accidents are caused.
Therefore, the lithium ion battery in the prior art has poor heavy impact performance, so that the lithium ion battery has low safety.
Disclosure of Invention
The embodiment of the invention aims to provide a battery and a preparation method of the battery, which solve the problem of lower safety of the battery in the prior art.
In order to achieve the above object, according to a first aspect, an embodiment of the present invention provides a battery, including a case, a battery cell, and an electrolyte, where the case accommodates the battery cell and the electrolyte; the battery cell comprises a positive plate, wherein a hole is formed in the positive plate; the electrolyte comprises a solid flame-retardant electrolyte, at least part of which is positioned in the pores of the positive plate;
wherein the solid state flame retardant electrolyte comprises an X group, X being as follows:
Figure SMS_1
。
alternatively, in the case where the electrolyte solution contains a flowable flame retardant electrolyte prior to formation, the flowable flame retardant electrolyte may be cured in situ to obtain the solid flame retardant electrolyte upon formation.
Alternatively, the solid flame retardant electrolyte is obtained by polymerizing monomers containing unsaturated double bond hydrocarbons in a multi-polymerization manner.
Optionally, the unsaturated double bond hydrocarbon-containing monomer includes at least one of a double bond-containing phosphate and a cyclic ether-containing phosphate.
Optionally, the reaction formula of the solid flame-retardant electrolyte is:
R1+R2+R3→R4；
wherein, R4 is the solid flame-retardant electrolyte, R1 is unsaturated esters containing c=c, R2 is esters containing c=c and c=o, and R3 is phosphate.
Alternatively, R1 comprises methacrylate, R2 comprises trifluoromethyl acrylate, and R3 comprises meepp.
Optionally, the lithium ion battery further comprises a negative plate, wherein a hole is formed in the negative plate, and a gap is formed between the positive plate and the negative plate;
wherein at least part of the solid state flame retardant electrolyte is located within the pores of the negative electrode sheet and/or at least part of the solid state flame retardant electrolyte is located within the gaps.
In a second aspect, an embodiment of the present invention provides a method for preparing a battery, including:
forming a positive plate, wherein a hole is formed in the positive plate;
forming an electric core, wherein the electric core comprises the positive plate;
forming a shell, and arranging the battery cell in the shell;
injecting electrolyte into the shell to obtain a battery;
wherein the electrolyte of the battery comprises a solid flame-retardant electrolyte, and at least part of the solid flame-retardant electrolyte is positioned in the pores of the positive plate; the solid flame retardant electrolyte comprises an X group, X being as follows:
Figure SMS_2
。
optionally, after the electrolyte is injected into the casing to obtain the battery, the method further includes:
forming the battery;
under the condition that the electrolyte contains the flowable flame-retardant electrolyte before formation, the flowable flame-retardant electrolyte can be cured in situ during formation to obtain the solid flame-retardant electrolyte.
Optionally, the content of the flowable flame retardant electrolyte in the electrolyte prior to formation is less than 10%.
One of the above technical solutions has the following advantages or beneficial effects:
in the embodiment of the invention, the solid flame-retardant electrolyte has certain flexibility and can improve the stretching rate of the positive plate. When the battery is impacted by a heavy object, the tensile resistance of the positive plate is enhanced, the probability of exposing the aluminum foil due to the impact of the heavy object is reduced, the risk of internal short circuit due to the contact of the positive aluminum foil and the negative graphite is further reduced, and the safety performance of the battery is improved.
Drawings
FIG. 1 is a schematic diagram of a positive plate according to an embodiment of the present invention;
FIG. 2 is a schematic illustration of a chemical reaction of a solid flame retardant electrolyte according to an embodiment of the present invention;
fig. 3 is a schematic flow chart of a method for manufacturing a battery according to an embodiment of the present invention;
fig. 4 is a schematic diagram of experimental results of each of examples and comparative examples provided in the examples of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides a battery, which comprises a shell, a battery core and electrolyte, wherein the shell accommodates the battery core and the electrolyte; the battery cell comprises a positive plate, wherein a hole is formed in the positive plate; the electrolyte comprises a solid flame-retardant electrolyte, at least part of which is positioned in the pores of the positive plate;
wherein the solid state flame retardant electrolyte comprises an X group, X being as follows:
Figure SMS_3
。
in the battery provided by the embodiment of the invention, as shown in fig. 1, a hole 110 is formed in a positive electrode sheet 100. The solid flame-retardant electrolyte exists in the pores, and has certain flexibility, so that the stretching rate of the positive plate can be improved. When the battery is impacted by a heavy object, the tensile resistance of the positive plate is enhanced, the probability of exposing the aluminum foil due to the impact of the heavy object is reduced, the risk of internal short circuit due to the contact of the positive aluminum foil and the negative graphite is further reduced, and the safety performance of the battery is improved. In addition, the X group has a strong polar bond, so that the stability of the solid flame-retardant electrolyte can be ensured, and the overall safety of the battery can be improved.
Alternatively, in the case where the electrolyte solution contains a flowable flame retardant electrolyte prior to formation, the flowable flame retardant electrolyte may be cured in situ to obtain the solid flame retardant electrolyte upon formation.
In this embodiment, when the battery needs to be charged and discharged by heating during the formation process, if the electrolyte solution contains a flowable flame-retardant electrolyte before formation, the flowable electrolyte may be cured in situ during formation to obtain the solid flame-retardant electrolyte. The formation process is a conventional process in the battery preparation process, so that no extra step or process is needed, the solid flame-retardant electrolyte can be obtained by solidifying the flowable flame-retardant electrolyte, the preparation process of the battery is simplified, the time consumed for preparing the battery is reduced, and the preparation efficiency of the battery is improved.
Due to the fluidity of the flowable electrolyte, after the electrolyte containing the flowable flame-retardant electrolyte is injected into the case, the flowable flame-retardant electrolyte may flow entirely into the pores of the positive electrode sheet, or may flow partially into the pores of the positive electrode sheet. Based on this, optionally, if the anode plate of the battery is formed with a hole, the anode plate and the anode plate are formed with a gap, and a part of the flowable flame-retardant electrolyte flows into the gap between the anode plate and the anode plate, even a part of the flowable flame-retardant electrolyte flows into the hole of the anode plate, then the solid flame-retardant electrolyte obtained by curing the flowable flame-retardant electrolyte is also partially located in the gap between the anode plate and the anode plate, and is partially located in the hole of the anode plate.
Alternatively, the solid flame retardant electrolyte is polymerized from monomers containing unsaturated double bond hydrocarbons and initiator polyols.
In the embodiment, the solid flame-retardant electrolyte can be prepared by adding an initiator into a multi-polymerization monomer to initiate multi-polymerization, so that the preparation process of the solid flame-retardant electrolyte is simpler.
In an alternative embodiment, the unsaturated double bond hydrocarbon-containing monomer includes at least one of a double bond-containing phosphate and a cyclic ether-containing phosphate. Wherein, alternatively, the double bond-containing phosphate may be obtained by radical polymerization, and the cyclic ether-containing phosphate may be obtained by cationic ring-opening polymerization, which may be specifically determined according to practical situations, and the embodiments of the present invention are not limited herein.
Optionally, the reaction formula of the solid flame-retardant electrolyte is:
R1+R2+R3→R4；
wherein, R4 is the solid flame-retardant electrolyte, R1 is unsaturated esters containing c=c, R2 is esters containing c=c and c=o, and R3 is phosphate. R4 also contains-COOCH 3 and-COOCH 2CF3.
In an alternative embodiment, R1 comprises methacrylate, R2 comprises trifluoromethyl acrylate, R3 comprises metapp, and the initiator is azobisisobutyronitrile (2, 2' -Azobis (AIBN).
In this embodiment, the fluid flame-retardant electrolyte may be obtained by initiating the multi-polymerization using a c=c-containing methacrylate (MMA), trifluoromethyl acrylate (TFMA), and meepp as the multi-polymerization monomer and Azobisisobutyronitrile (AIBN) as the initiator. The fluidity electrolyte prepared in this way can be solidified to obtain the phosphate-based flame-retardant polymer electrolyte after heating and polymerization, and the specific chemical reaction formula is shown in figure 2. The phosphate-based flame-retardant polymer electrolyte is a solid electrolyte which is gel, has stronger flexibility, and can further enhance the tensile resistance of the positive plate, further enhance the heavy-load impact resistance of the battery and further enhance the safety performance of the battery.
Referring to fig. 3, fig. 3 is a flowchart of a method for manufacturing a battery according to an embodiment of the invention. As shown in fig. 3, the preparation method of the battery includes:
step 301, forming a positive plate, wherein a hole is formed in the positive plate;
step 302, forming a battery cell based on the positive electrode sheet;
step 303, forming a shell, and arranging the battery cell in the shell;
step 304, injecting electrolyte into the shell to obtain a battery;
wherein the electrolyte of the battery comprises a solid flame-retardant electrolyte, and at least part of the solid flame-retardant electrolyte is positioned in the pores of the positive plate; the solid flame retardant electrolyte comprises an X group, X being as follows:
Figure SMS_4
。
in the embodiment of the invention, the solid flame-retardant electrolyte has certain flexibility and can improve the stretching rate of the positive plate. When the battery is impacted by a heavy object, the tensile resistance of the positive plate is enhanced, the probability of exposing the aluminum foil due to the impact of the heavy object is reduced, the risk of internal short circuit due to the contact of the positive aluminum foil and the negative graphite is further reduced, and the safety performance of the battery is improved. In addition, the X group has a strong polar bond, so that the stability of the solid flame-retardant electrolyte can be ensured, and the overall safety of the battery can be improved.
In specific implementation, the positive plate can be prepared according to the following steps:
1) And preparing positive electrode slurry. The positive electrode slurry may be formed by mixing a positive electrode active material, a conductive agent, a binder, and a solvent. Wherein the positive electrode active material may include at least one of lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickelate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, wherein the particle diameter D50 may be 5 μm to 20 μm, and the conductive agent may include at least one of conductive graphite, ultrafine graphite, acetylene black, conductive carbon black SP, superconducting carbon black, carbon nanotubes, and conductive carbon fibers. The binder may include at least one of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethyl cellulose, styrene-butadiene rubber, polyurethane, polyvinyl alcohol, polyvinylidene fluoride, and a copolymer of vinylidene fluoride-fluorinated olefin. The solvent may include at least one of toluene, xylene, methanol, ethanol, acetone, tetrahydrofuran, N-methylpyrrolidone, NMP, and water.
2) And coating the positive electrode slurry on a positive electrode current collector by using a double-layer coating machine, drying at 120 ℃, and carrying out the procedures of slitting, tabletting and the like to obtain the positive electrode plate.
The negative electrode sheet can be prepared according to the following steps:
1) And preparing negative electrode slurry. The negative electrode slurry may be formed by mixing a negative electrode active material, a conductive agent, a binder, a thickener, and a solvent. The negative active material may include at least one of natural graphite, artificial graphite, silicon carbon, and lithium titanate, the thickener may include a resin binder including at least one of phenolic resin, polyacrylic resin, polyurethane resin, and epoxy resin, and the conductive agent, the binder, and the solvent may be referred to the above description and will not be repeated herein.
2) The negative electrode slurry was coated onto a negative electrode current collector using a double-layer coater. And then drying at 120 ℃, and carrying out the procedures of slitting, tabletting and the like to obtain the positive plate.
And then, preparing the prepared positive plate and negative plate together with a diaphragm and an aluminum plastic film (shell) into a battery, and then performing the procedures of liquid injection, aging, formation, pre-circulation and the like to prepare the battery.
Optionally, after the electrolyte is injected into the casing to obtain the battery, the method further includes:
forming the battery;
under the condition that the electrolyte contains the flowable flame-retardant electrolyte before formation, the flowable flame-retardant electrolyte can be cured in situ during formation to obtain the solid flame-retardant electrolyte.
In this embodiment, when the battery needs to be charged and discharged by heating during the formation process, if the electrolyte solution contains a flowable flame-retardant electrolyte before formation, the flowable electrolyte may be cured in situ during formation to obtain the solid flame-retardant electrolyte. The formation process is a conventional process in the battery preparation process, so that no extra step or process is needed, the solid flame-retardant electrolyte can be obtained by solidifying the flowable flame-retardant electrolyte, the preparation process of the battery is simplified, the time consumed for preparing the battery is reduced, and the preparation efficiency of the battery is improved. In addition, the electrolyte added with the flowable flame-retardant electrolyte still has strong ionic conductivity, so the electrical performance of the battery is not basically affected.
In particular, by adding a flowable flame retardant electrolyte to the electrolyte when the housing is injected, optionally, a flowable flame retardant electrolyte having a content of less than 10% may be added. Based on the fluidity of the flowable flame retardant electrolyte, at least a portion of the flowable flame retardant electrolyte may fill in the pores of the positive electrode sheet.
In addition, due to the fluidity of the flowable electrolyte, after the electrolyte containing the flowable flame-retardant electrolyte is injected into the housing, the flowable flame-retardant electrolyte may flow into the pores of the positive electrode sheet entirely, may flow into the pores of the positive electrode sheet partially, may flow into the gaps between the positive electrode sheet and the negative electrode sheet partially, and may even flow into the pores of the negative electrode sheet partially.
Several specific examples of embodiments of the present invention and comparative examples are described below.
Examples
In this embodiment, the preparation process of the battery is specifically as follows:
step one, preparing a positive plate
The method comprises the steps of taking lithium cobaltate as an anode active material, taking conductive carbon nano tubes as a conductive agent, taking polyvinylidene fluoride as a binder, adding the conductive carbon nano tubes into a stirring tank, and then adding N-methyl pyrrolidone, stirring and dispersing to prepare anode slurry, wherein the solid components in the anode slurry comprise 97.8wt% of lithium cobaltate (LiCoO 2), 1.1 wt% of conductive carbon black and 1.1 wt% of polyvinylidene fluoride (PVDF). And coating the positive electrode slurry on the surface of a positive electrode current collector by adopting a double-sided coating technology, and then performing procedures such as drying, slitting, tabletting and the like to prepare the positive electrode plate. The preparation environment temperature of the anode electrode material is kept at 20-30 ℃, and the humidity is less than or equal to 40% RH. The equipment used for preparing the positive electrode material comprises: stirring machine, coating machine, roller press, cutting machine, pelleter, ultrasonic spot welding machine, top side sealing machine, ink jet numbering machine, film sticking machine, liquid injecting machine, formation cabinet, cold press, sorting cabinet, vacuum oven, etc.
Step two, preparing a negative plate
Artificial graphite is used as a negative electrode active material, conductive carbon black is used as a conductive agent, styrene-butadiene rubber is used as an adhesive, sodium carboxymethyl cellulose is used as a thickening agent, and the negative electrode slurry is prepared by adding deionized water into a stirring tank, stirring and dispersing. The solid components in the negative electrode slurry contained 96.9% artificial graphite, 0.5% conductive carbon black, 1.3% sodium carboxymethylcellulose (Carboxy-methyl cellulose sodium, CMC-Na), 1.3% styrene-butadiene rubber (Polymerized Styrene Butadiene Rubber, SBR). And coating the negative electrode slurry on the surface of a negative electrode current collector by adopting a double-sided coating technology, and then performing procedures such as drying, slitting, tabletting and the like to prepare the negative electrode plate. The preparation environment temperature of the negative electrode material is kept at 20-30 ℃, and the humidity is less than or equal to 40% RH. The equipment used for preparing the negative electrode material comprises the following components: stirring machine, coating machine, roller press, cutting machine, pelleter, ultrasonic spot welding machine, top side sealing machine, ink jet numbering machine, film sticking machine, liquid injecting machine, formation cabinet, cold press, sorting cabinet, vacuum oven, etc.
Step three, preparing the fluidity flame-retardant electrolyte
And (3) performing multi-polymerization reaction by using methacrylic acid ester (MMA), trifluoro methacrylic acid ester (TFMA) and METEPP containing C=C as multi-polymerization monomers and azo-bis-isobutyronitrile (AIBN) as an initiator to obtain the flowable flame-retardant electrolyte.
Step four, preparing a battery and injecting liquid
And (3) preparing the positive plate prepared in the step one and the negative plate prepared in the step two into a battery together with a diaphragm and an aluminum plastic film (a shell), and then performing a liquid injection procedure, namely injecting electrolyte containing 5% of fluidity flame-retardant electrolyte into the shell.
Step five, formation and in-situ solidification
And (3) performing a formation process on the battery after the liquid injection process is completed in the step (IV), wherein in the formation process, the flowable flame-retardant electrolyte is heated and polymerized to obtain the solid phosphate-based flame-retardant polymer electrolyte.
Examples
Example 2 differs from example 1 in that an electrolyte containing 2.5% of a flowable flame-retardant electrolyte was injected into the case during the injection process. Other steps and descriptions may refer to the description of embodiment 1, and are not repeated here.
Examples
Example 3 is different from example 1 in that an electrolyte containing 7.5% of a flowable flame-retardant electrolyte is injected into the case during the injection process. Other steps and descriptions may refer to the description of embodiment 1, and are not repeated here.
Comparative example 1
Comparative example 1 is different from example 1 in that a conventional electrolyte, that is, an electrolyte containing 0% of a flowable flame-retardant electrolyte, is injected into the case during the injection process. Other steps and descriptions may refer to the description of embodiment 1, and are not repeated here.
The batteries of examples 1 to 3 and comparative example 1 were respectively subjected to tests for electrochemical performance and safety performance (mainly heavy impact). The specific test contents are as follows:
1) Weight impact test: the batteries of examples 1 to 3 and comparative example 1 were subjected to a needling test as follows: after the battery is fully charged according to a standard charging system, a metal rod with the diameter of 15.8mm plus or minus 0.2mm is transversely arranged on the upper surface of the geometric center of the battery, and a weight with the mass of 9.1kg is adopted to strike the surface of the battery with the metal rod from a state of free falling at a height of 610mm, so that the battery is free from firing and explosion.
2) And (3) cyclic test: the battery was placed in a constant temperature room at 25C, discharged to a lower limit voltage at 0.7C, charged to an upper limit voltage at 1.5C, and discharged to a lower limit voltage at 1C, and the capacity retention rate of the battery was calculated by cycling for 800 weeks.
3) Pole piece elongation test: and clamping the two ends of the rolled pole piece by using a testing instrument, recording the initial distance between the two ends as L1, starting to stretch the pole piece by applying force by the instrument, recording the distance between the two ends as L2 when the pole piece breaks, and calculating the elongation percentage by using a formula of (L2-L1)/L1.
Finally, the results of the safety test are summarized in table 1 and fig. 4. As can be seen from the results in Table 1, the weight impact test of comparative example 1 has a low pass rate, i.e., low safety, and cannot meet the safety performance requirements of lithium ion batteries. The passing rate of the weight impact experiments of the examples 1 to 3 is higher than that of the comparative example 1, so that the safety of the lithium ion battery is effectively improved. In addition, the cycle retention rate and the needling passage rate of example 1 are more preferable, and example 1 may be preferably selected in practical applications.
Table 1 safety test results for different examples and comparative examples
Weight impact pass rate Constant temperature cycle capacity retention rate/800T Addition amount of flowable flame-retardant electrolyte Elongation percentage of positive plate
Example 1 10/10 PASS 85.83% 5% 10%
Example 2 6/10 PASS 86.56% 2.5% 8%
Example 3 10/10 PASS 75.90% 7.5% 11%
Comparative example 1 0/10 PASS 89.62% 0% 3%
It should be noted that, the various alternative embodiments described in the embodiments of the present invention may be implemented in combination with each other, or may be implemented separately, which is not limited to the embodiments of the present invention.
In the description of the present invention, it should be understood that the terms "upper," "lower," "left," "right," and the like indicate an orientation or a positional relationship based on that shown in the drawings, and are merely for convenience of description and for simplifying the description, and do not indicate or imply that the apparatus or element in question must have a specific orientation, as well as a specific orientation configuration and operation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and the like are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
The embodiments described above are described with reference to the drawings, and other different forms and embodiments are possible without departing from the principle of the invention, and therefore, the invention should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will convey the scope of the invention to those skilled in the art. In the drawings, component dimensions and relative dimensions may be exaggerated for clarity. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. The terms "comprises," "comprising," and/or "includes," when used in this specification, specify the presence of stated features, integers, components, and/or groups thereof, but do not preclude the presence or addition of one or more other features, integers, components, and/or groups thereof. Unless otherwise indicated, a range of values includes the upper and lower limits of the range and any subranges therebetween.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and changes can be made without departing from the principles of the present invention, and such modifications and changes are intended to be within the scope of the present invention.

Claims (6)

1. The battery is characterized by being a lithium ion battery, and comprises a shell, an electric core and electrolyte, wherein the electric core and the electrolyte are contained in the shell; the battery cell comprises a positive plate and a negative plate, wherein a hole is formed in the positive plate; the electrolyte comprises a solid flame-retardant electrolyte, at least part of which is positioned in the pores of the positive plate; the anode plate is provided with a hole, and a gap is formed between the anode plate and the anode plate;
wherein at least part of the solid state flame retardant electrolyte is located within the pores of the negative electrode sheet and/or at least part of the solid state flame retardant electrolyte is located within the gaps; the content of the flowing flame-retardant electrolyte in the electrolyte before formation is less than 10%;
in the formation process, the flowable flame-retardant electrolyte is cured in situ to obtain the solid flame-retardant electrolyte;
wherein the solid state flame retardant electrolyte comprises an X group, X being as follows:
Figure QLYQS_1
。
2. the battery of claim 1, wherein the solid state flame retardant electrolyte is obtained by initiated polymerization of monomers containing unsaturated double bond hydrocarbons.
3. The battery of claim 2, wherein the unsaturated double bond hydrocarbon-containing monomer comprises at least one of a double bond-containing phosphate and a cyclic ether-containing phosphate.
4. The battery of claim 1, wherein the solid state flame retardant electrolyte has a reaction formula:
R1+R2+R3→R4；
wherein, R4 is the solid flame-retardant electrolyte, R1 is unsaturated esters containing c=c, R2 is esters containing c=c and c=o, and R3 is phosphate.
5. The battery of claim 4, wherein R1 comprises a methacrylate, R2 comprises a trifluoromethyl acrylate, R3 comprises METEPP,
the structural formula of METEPP is as follows:
Figure QLYQS_2
。
6. a method of making a battery, wherein the battery is a lithium ion battery, the method comprising:
forming a positive plate, wherein a hole is formed in the positive plate;
forming a negative plate, wherein a hole is formed in the negative plate; a gap is formed between the positive electrode plate and the negative electrode plate;
forming an electric core, wherein the electric core comprises the positive electrode plate and the negative electrode plate;
forming a shell, and arranging the battery cell in the shell;
injecting electrolyte into the shell to obtain a battery;
forming the battery;
the content of the flowing flame-retardant electrolyte in the electrolyte before formation is less than 10%;
the flowable flame-retardant electrolyte is cured in situ during formation to obtain a solid flame-retardant electrolyte;
the electrolyte of the battery comprises the solid flame-retardant electrolyte, and at least part of the solid flame-retardant electrolyte is positioned in the pores of the positive plate; at least a portion of the solid state flame retardant electrolyte is located within the pores of the negative electrode sheet and/or at least a portion of the solid state flame retardant electrolyte is located within the interstices; the solid flame retardant electrolyte comprises an X group, X being as follows:
Figure QLYQS_3
。
CN202110704327.7A 2021-06-24 2021-06-24 Battery and preparation method thereof Active CN113437352B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110704327.7A CN113437352B (en) 2021-06-24 2021-06-24 Battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110704327.7A CN113437352B (en) 2021-06-24 2021-06-24 Battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113437352A CN113437352A (en) 2021-09-24
CN113437352B true CN113437352B (en) 2023-06-20

Family

ID=77753924

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110704327.7A Active CN113437352B (en) 2021-06-24 2021-06-24 Battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113437352B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108258323A (en) * 2018-01-30 2018-07-06 陕西煤业化工技术研究院有限责任公司 A kind of production method of high specific energy solid lithium battery
CN110048153A (en) * 2019-05-06 2019-07-23 浙江大学 A kind of solid metallic lithium battery and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013134566A2 (en) * 2012-03-07 2013-09-12 Massachusetts Institute Of Technology Rechargeable lithium battery for wide temperature operation
CN106450442B (en) * 2016-09-27 2020-02-11 湖南杉杉能源科技股份有限公司 Flame-retardant gel electrolyte for lithium ion battery, preparation method of flame-retardant gel electrolyte and preparation method of lithium ion battery
CN108417777B (en) * 2018-04-28 2021-02-19 苏州清陶新能源科技有限公司 Porous ternary composite positive plate and preparation method and application thereof
CN109671977A (en) * 2018-12-17 2019-04-23 深圳先进技术研究院 Flame-retardant polymer gel electrolyte and preparation method thereof, lithium battery
CN110429329A (en) * 2019-08-15 2019-11-08 湖南立方新能源科技有限责任公司 A kind of preparation method and all-solid sodium ion battery of all-solid sodium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108258323A (en) * 2018-01-30 2018-07-06 陕西煤业化工技术研究院有限责任公司 A kind of production method of high specific energy solid lithium battery
CN110048153A (en) * 2019-05-06 2019-07-23 浙江大学 A kind of solid metallic lithium battery and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Novel safer phosphonate-based gel polymer electrolytes for sodium-ion batteries with excellent cycling performance;Jinyun Zheng et al;《Journal of Materials Chemistry A》;20180328;第6卷;第6559-6564页 *

Also Published As

Publication number Publication date
CN113437352A (en) 2021-09-24

Similar Documents

Publication Publication Date Title
CN110660965B (en) Negative plate and preparation method thereof, lithium ion battery and preparation method and application thereof
CN106486639B (en) A kind of lithium battery pole slice and preparation method thereof
TW529190B (en) Polymer electrolyte battery and method of producing the same
US8277977B2 (en) Binder composition, slurry for electrodes, electrode and nonaqueous electrolyte secondary battery
JP5133111B2 (en) Lithium ion capacitor
CN114665065B (en) Positive electrode plate and preparation method and application thereof
JP2012531020A (en) Lithium ion battery
JPWO2012086340A1 (en) Electric storage device, lithium ion capacitor, and negative electrode for lithium ion capacitor
CN114583100A (en) Positive plate, preparation method thereof and lithium ion battery
CN114824259A (en) Lithium ion battery composite positive plate, preparation method thereof and lithium ion battery
CN114373887A (en) Lithium ion battery, lithium ion battery positive plate and preparation method thereof
CN112688022A (en) Quick charge-discharge lithium ion battery and preparation method thereof
CN112736247A (en) Water-based composite binder, negative electrode slurry and preparation method thereof, negative electrode sheet, lithium ion battery cell, lithium ion battery pack and application thereof
CN101826640B (en) Pole core for lithium ion battery and lithium ion battery using pole core
CN111463433B (en) Ultrahigh-rate lithium iron phosphate battery and preparation method thereof
CN117334830A (en) Positive plate and lithium ion battery
CN108695558B (en) All-solid-state battery core and high-performance solid-state battery comprising same
KR20160113582A (en) Electrode for electrochemical elements, and electrochemical element
CN113728504B (en) Polymer binder, laminated porous film, battery, and electronic device
CN112151757B (en) Negative plate with multilayer film structure and mixed solid-liquid electrolyte lithium storage battery thereof
CN111916835B (en) Polymer lithium ion battery and preparation method thereof
CN111430779B (en) Electrolyte raw material composition, electrolyte, lithium ion secondary battery and preparation method thereof
CN219180585U (en) Secondary battery
CN113437352B (en) Battery and preparation method thereof
CN114023952B (en) Positive active material, positive plate and lithium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant