CN113707971A - Preparation method of high-safety battery and battery - Google Patents
Preparation method of high-safety battery and battery Download PDFInfo
- Publication number
- CN113707971A CN113707971A CN202110990157.3A CN202110990157A CN113707971A CN 113707971 A CN113707971 A CN 113707971A CN 202110990157 A CN202110990157 A CN 202110990157A CN 113707971 A CN113707971 A CN 113707971A
- Authority
- CN
- China
- Prior art keywords
- safety
- battery
- shell
- inhibitor
- electrolyte
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003063 flame retardant Substances 0.000 claims abstract description 70
- 239000003792 electrolyte Substances 0.000 claims abstract description 64
- 239000003112 inhibitor Substances 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000000977 initiatory effect Effects 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000002844 melting Methods 0.000 claims description 37
- 230000008018 melting Effects 0.000 claims description 37
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 27
- 229910045601 alloy Inorganic materials 0.000 claims description 26
- 239000000956 alloy Substances 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 18
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 claims description 18
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000004698 Polyethylene Substances 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 15
- 229920000573 polyethylene Polymers 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 238000003487 electrochemical reaction Methods 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 11
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 229920006122 polyamide resin Polymers 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000005077 polysulfide Substances 0.000 claims description 8
- 229920001021 polysulfide Polymers 0.000 claims description 8
- 150000008117 polysulfides Polymers 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 239000001993 wax Substances 0.000 claims description 8
- WVSNNWIIMPNRDB-UHFFFAOYSA-N 1,1,1,3,3,4,4,5,5,6,6,6-dodecafluorohexan-2-one Chemical compound FC(F)(F)C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WVSNNWIIMPNRDB-UHFFFAOYSA-N 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002050 silicone resin Polymers 0.000 claims description 5
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- 229910052744 lithium Inorganic materials 0.000 description 18
- 150000003254 radicals Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000004880 explosion Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007760 free radical scavenging Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000009516 primary packaging Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
-
- 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
-
- 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
- H01M10/60—Heating or cooling; Temperature control
- H01M10/61—Types of temperature control
- H01M10/613—Cooling or keeping cold
-
- 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
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
- H01M10/6567—Liquids
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Mounting, Suspending (AREA)
Abstract
The invention belongs to the technical field of batteries and discloses a preparation method of a high-safety battery and the batteryh1Therefore, the temperature in the electric core module reaches the thermal runaway initiation temperature Th1Before the high-safety structure shell body is started to be in a molten state, and the inhibitor, fire retardant and fire extinguishing agent are gradually added along with the rise of temperature in the batteryThe electrolyte is released in the step to inhibit the thermal runaway phenomenon in stages and improve the safety performance. Because the shell with the high-safety structure can cover the inhibitor, the flame retardant and the fire extinguishing agent inside, liquid cannot seep into the electrolyte when the battery works normally, and the performances of the battery such as multiplying power, circulation and the like cannot be influenced.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method of a high-safety battery and the battery.
Background
Lithium batteries have been widely used in the fields of consumer digital products, energy storage power stations, electric bicycles, electric vehicles, and the like, due to their outstanding advantages of high energy density, low self-discharge, no memory effect, and the like. A common failure of a lithium battery is thermal runaway, which mainly results from overcharge or overdischarge of a battery cell, conductive particles inside the battery cell, a defect of a solid-electrolyte membrane, and an over-high temperature of the battery cell. In recent years, accidents such as explosion or fire caused by thermal runaway of a lithium battery of an electric automobile emerge endlessly, and the life and property safety of users are seriously threatened.
Therefore, while the energy density of the lithium battery is improved and the unit volume of the lithium battery is ensured to have high storage capacity, the occurrence of thermal runaway faults of the lithium battery needs to be avoided as much as possible. The existing method for improving the energy density of the lithium battery is to continuously increase the content of Ni element in the lithium battery and simultaneously reduce the content of Co element, and the main defects are as follows: along with the increase of the content of the Ni element and the reduction of the content of the Co element, the stability of the battery core anode material is reduced, and the temperature sequence of the thermal decomposition of the currently commonly used anode material is as follows: NCM811(175 ℃) < NCM622(178 ℃) < NCM523(183 ℃) < NCM111(199 ℃) < LiCoO2(200 ℃) < LiMn2O4(220 ℃) < LiFePO4(250 ℃), that is, the existing method for improving the energy density of the lithium battery can reduce the thermal runaway initiation temperature of the battery cell and reduce the safety.
The existing method for reducing the thermal runaway probability of the lithium battery is to add a flame retardant into the battery electrolyte. Electrolytes commonly used in lithium batteries are based on the dissolution of a lithium salt in cyclic or linear carbonates, such as Ethylene Carbonate (EC) + dimethyl carbonate (DMC), these ester electrolytes being highly volatile and flammable, and having a flash point close to room temperature. In the thermal runaway state of the battery, the combustion of the electrolyte and even the explosion of the battery can be caused. The addition of the flame retardant into the electrolyte can improve the oxygen index of the electrolyte and reduce the flammability of the electrolyte, but can affect the multiplying power, the cycle and other performances of a battery cell and reduce the discharge specific capacity of the battery, and the durability of the battery after single charging is lower.
Disclosure of Invention
The invention aims to provide a preparation method of a high-safety battery and the battery, which can effectively reduce heat generated in a battery cell module, inhibit thermal runaway of the battery cell module and improve safety on the premise of not influencing the multiplying power, circulation and other properties of the battery cell module.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, a method for preparing a high-safety battery is provided, which comprises the following steps:
manufacturing a shell with a high safety structure: the melting point of the casing of the high-safety structure is lower than the thermal runaway initiation temperature T of the batteryh1；
Injecting an inhibitor, a fire retardant and a fire extinguishing agent into the high safety structure housing: the inhibitor is used for inhibiting the movement of lithium ions in the electrolyte, the fire retardant is used for removing inflammable free radicals generated by electrochemical reaction in the electrolyte, the fire extinguishing agent is used for absorbing heat generated by the electrochemical reaction, and the inhibitor, the fire retardant and the fire extinguishing agent are mutually immiscible;
assembling the battery cell module: installing a naked electric core in a shell of the electric core module, installing the high-safety structure in the naked electric core, injecting electrolyte into the shell of the electric core module and packaging the electric core module;
and assembling the circuit board and the plurality of battery cell modules to form the high-safety battery.
In a preferred embodiment of the method for producing a high-safety battery according to the present invention, the case of the high-safety structure has a first molten state, a second molten state, and a third molten state, and the self-exothermic starting temperature of the battery is Th0；
The temperature of the electrolyte reaches T1When the high-safety structure shell is melted to a first molten state, the inhibitor is released from the high-safety structure shell;
the temperature of the electrolyte reaches T2When the high-safety structure shell is melted to a second molten state, the flame retardant is released from the high-safety structure shell;
the temperature of the electrolyte reaches T3When the fire extinguishing agent is released from the shell of the high-safety structure, the shell of the high-safety structure is melted to a third molten state;
Th0＜T1＜T2＜T3＜Th1。
as a preferable embodiment of the method for manufacturing a high-safety battery provided by the present invention, the inhibitor includes Dibenzylamine (DBA), Benzylamine (BA), and Trihexylamine (THA), the flame retardant includes trimethyl phosphate (TMP) and/or triphenyl phosphate (TPP), and the fire extinguishing agent includes perfluorohexanone.
As a preferable embodiment of the method for manufacturing a high-safety battery provided by the present invention, the case of the high-safety structure includes one or more of polyethylene wax, polyethylene, polyurethane, polyamide resin, polysulfide rubber, phenolic resin, epoxy resin, vinyl resin, and silicone resin.
As a preferable scheme of the preparation method of the high-safety battery provided by the invention, the proportion of dibenzylamine in the inhibitor is 50-70%, the proportion of benzylamine is 15-25%, and the proportion of trihexylamine is 15-25%, the flame retardant is trimethyl phosphate, and the proportion of the inhibitor, the flame retardant and the fire extinguishing agent is 0.6: 0.2: 0.2.
as a preferable scheme of the preparation method of the high-safety battery provided by the invention, two high-safety structures are manufactured, and the two high-safety structures are both installed on the same bare cell, wherein a shell of one high-safety structure is an alloy safety shell, a shell of the other high-safety structure is a polymer safety shell, the alloy safety shell comprises one or more of bismuth, lead, tin and cadmium, and the polymer safety shell comprises one or more of polyethylene wax, polyethylene, polyurethane, polyamide resin, polysulfide rubber, phenolic resin, epoxy resin, vinyl resin and silicone resin.
As a preferable scheme of the preparation method of the high-safety battery provided by the invention, the melting point of the alloy safety shell is M1Said polymeric safety shell having a melting point M2，M1≠M2In the inhibitor, the percentage of dibenzylamine is 10% -15%, the percentage of benzylamine is 10% -15%, and the percentage of trihexylamine is 70% -80%, the flame retardant is triphenyl phosphate, and the ratio of the inhibitor, the flame retardant and the fire extinguishing agent is 0.5: 0.4: 0.1.
as a preferable scheme of the preparation method of the high-safety battery provided by the invention, the melting point of the alloy safety shell is M3Said polymeric safety shell having a melting point M4，M3≠M4In the inhibitor, the percentage of dibenzylamine is 10% -15%, the percentage of benzylamine is 10% -15%, and the percentage of trihexylamine is 70% -80%, the flame retardant is triphenyl phosphate, and the ratio of the inhibitor, the flame retardant and the fire extinguishing agent is 0.3: 0.3: 0.4.
as a preferable scheme of the method for manufacturing a high-safety battery provided by the invention, the alloy safety shell comprises an adaptor sheet in the electric core module, and the polymer safety shell comprises a lower plastic piece in the electric core module.
In another aspect, there is provided a battery manufactured by the method for manufacturing a high safety battery as described above, including:
the battery cell module comprises a plurality of battery cell modules, wherein a naked battery cell is arranged in a shell of each battery cell module and is filled with electrolyte;
the high-safety structure is arranged in the naked electric core and soaked in the electrolyte, a shell of the high-safety structure defines a liquid storage cavity, an inhibitor, a fire retardant and a fire extinguishing agent are stored in the liquid storage cavity, and the melting point of the shell of the high-safety structure is lower than the thermal runaway initiation temperature T of the batteryh1The inhibitor, the fire retardant and the fire extinguishing agent are sequentially released into the electrolyte as the temperature in the electric core module increases.
The invention has the beneficial effects that:
according to the preparation method of the high-safety battery provided by the invention, the high-safety structure is arranged on the naked battery core of the battery core module, the high-safety structure and the naked battery core are arranged in the shell of the battery core module, the electrolyte is injected into the shell of the battery core module and the shell of the battery core module is packaged, so that a complete battery core module is formed, and the preparation method is simple to manufacture. Three mutually immiscible liquids of an inhibitor, a fire retardant and a fire extinguishing agent are stored in the shell of the high-safety structure, and the melting point of the shell of the high-safety structure is lower than the thermal runaway initiation temperature T of the batteryh1Therefore, the temperature in the electric core module reaches the thermal runaway initiation temperature Th1Before, the casing of high-safety structure just begins to get into the molten state, afterwards, the inhibitor is at first released in the electrolyte from the casing, be used for hindering the migration of lithium ion between positive negative pole, thereby reduce the production of heat, along with the continuation rising of temperature, fire retardant and fire extinguishing agent release in the electrolyte in proper order, the fire retardant can clear away the inflammable free radical that electrochemical reaction produced in the electrolyte, such as hydrogen or oxyhydrogen active free radical, in order to reduce the possibility that takes place the flash of fire, the fire extinguishing agent is through absorbing the heat that electrochemical reaction produced, in order to reduce the temperature that will take place the position of flash of fire, thereby eliminate the phenomenon of flash of fire, reduce the probability that the battery catches fire or explodes, effectively improve battery security. Because the casing of high-safety structure can wrap the internal inhibitor, flame retardant and fire extinguishing agent, when the battery works normally, liquid cannot seep into electrolyte, so that the multiplying power, circulation and other performances of the battery cannot be influenced, and when the temperature in the battery cell module rises to a high-safety junctionWhen the shell is at the melting point, the inhibitor, the fire retardant and the fire extinguishing agent are gradually released, so that the thermal runaway phenomenon is inhibited in stages, and the safety performance is improved.
In the battery provided by the invention, the naked battery core of each battery core module is provided with the high-safety structure, the shell of the high-safety structure can cover the internal inhibitor, the flame retardant and the fire extinguishing agent, and when the battery works normally, liquid cannot seep into the electrolyte, so that the multiplying power, the circulation and other performances of the battery cannot be influenced.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a high safety battery according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention. It should be further noted that, for the convenience of description, only some of the structures related to the present invention are shown in the drawings, not all of the structures.
In the description of the present invention, unless expressly stated or limited otherwise, the terms "connected," "connected," and "fixed" are to be construed broadly, e.g., as meaning permanently connected, removably connected, or integral to one another; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In the present invention, unless otherwise expressly stated or limited, "above" or "below" a first feature means that the first and second features are in direct contact, or that the first and second features are not in direct contact but are in contact with each other via another feature therebetween. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly under and obliquely below the second feature, or simply meaning that the first feature is at a lesser elevation than the second feature.
In the description of the present embodiment, the terms "upper", "lower", "left", "right", and the like are used based on the orientations and positional relationships shown in the drawings only for convenience of description and simplification of operation, and do not indicate or imply that the referred device or element must have a specific orientation, be configured and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used only for descriptive purposes and are not intended to have a special meaning.
Example one
As shown in fig. 1, the embodiment provides a method for preparing a high-safety battery, which specifically includes the following steps:
manufacturing a shell with a high safety structure: the melting point of the case of the high safety structure is lower than the thermal runaway initiation temperature T of the batteryh1；
Injecting inhibitor, fire retardant and fire extinguishing agent into the shell of the high safety structure: the inhibitor is used for inhibiting the movement of lithium ions in the electrolyte, the flame retardant is used for removing inflammable free radicals generated by electrochemical reaction in the electrolyte, and the fire extinguishing agent is used for absorbing heat generated by the electrochemical reaction;
assembling the battery cell module: assembling a high-safety structure and a naked battery cell, installing the naked battery cell in a shell of a battery cell module, injecting electrolyte and packaging the shell of the battery cell module;
and assembling the circuit board and the plurality of battery cell modules to form the high-safety battery.
The manufacturing process of the bare cell comprises the procedures of slurry mixing, coating, rolling, slitting, die cutting, winding, ultrasonic welding and the like so as to ensure the qualification rate of the bare cell.
Optionally, the specific steps of assembling the battery cell module are as follows:
s1, installing the naked battery cell into a shell of the battery cell module;
s2, assembling the high-safety structure and the naked battery cell;
s3, laser welding the shell gap of the core module to finish primary packaging;
s4, baking the battery cell module to enhance the sealing performance and strength of the battery cell module;
s5, injecting electrolyte through a liquid injection port reserved on the battery cell module shell;
s6, plugging the liquid injection port;
and S7, carrying out formation, aging and grading procedures to complete the manufacture of the whole battery cell module.
In this embodiment, pack into the casing of electric core module with naked electric core earlier, accomplish the installation of high security structure and naked electric core again, step S1 goes on before step S2 promptly, and the purpose makes naked electric core and high security structure successively put into the casing of electric core module, accomplishes the installation in the casing, avoids the two to assemble the back because occupation space is great and can't pack into the casing of electric core module.
The process of thermal runaway of lithium batteries mainly comprises the following stages. The first stage is as follows: the solid-electrolyte separator (SEI film) on the surface of the negative electrode graphite is decomposed, and the process is carried out at 90-120 ℃. After the SEI film starts to decompose, the negative active material contacts the electrolyte to undergo an exothermic reaction, which provides conditions for the following series of side reactions. And a second stage: the electrolyte and the negative active material undergo a violent exothermic reaction, which also accelerates the temperature rise of the lithium battery. And a third stage: when the temperature of the lithium battery exceeds 120 ℃, the SEI film starts to break, which causes the contact short circuit of the positive electrode and the negative electrode to release a large amount of heat, and at the same time, the active material of the positive electrode starts to decompose, thereby generating oxygen and generating an exothermic reaction with the electrolyte. The temperature sequence of the thermal decomposition of the currently commonly used positive electrode material is as follows: NCM811(175 ℃ C.) < NCM622(178 ℃ C.) < NCM523(183 ℃ C.) < NCM111(199 ℃ C.) < LiCoO2(200 ℃ C.) < LiMn2O4(220 ℃ C.) < LiFePO4(250 ℃ C.). With the increase of the content of the Ni element and the decrease of the content of the Co element, the stability of the positive electrode material of the battery core is reduced, that is, the method for increasing the energy density of the lithium battery can reduce the temperature caused by thermal runaway of the battery core and the safety is reduced by increasing the content of the Ni element and simultaneously reducing the content of the Co element. A fourth stage: the lithium salt in the electrolyte is dissolved in the organic ester solvent, and when the temperature exceeds 200 ℃, the lithium salt and the solvent begin to decompose and release heat, so that the electrolyte is combusted, and the battery is exploded. That is, sudden heat generation, which is suddenly induced by slow heat generation, is a key to thermal runaway of the battery.
The preparation method of the high-safety battery provided by the embodiment can effectively reduce the heat generated in the battery, slow down the heat generation speed, avoid the decomposition of the positive active material and prevent the explosion of the battery while ensuring that the battery has high energy density.
Three immiscible liquids of an inhibitor, a fire retardant and a fire extinguishing agent are stored in the shell of the high-safety structure, and the melting point of the shell of the high-safety structure is lower than the thermal runaway initiation temperature T of the batteryh1Therefore, the temperature in the electric core module reaches the thermal runaway initiation temperature Th1The high-safety shell is then brought into a molten state. Subsequently, the inhibitor is first released from the case into the electrolyte for hindering the migration of lithium ions between the positive and negative electrodes, thereby reducing the generation of heat. As the temperature continues to rise, the fire retardant and the fire extinguishing agent are sequentially released into the electrolyte, and the fire retardant can remove inflammable free radicals generated by electrochemical reaction in the electrolyte, such as hydrogen or hydroxyl active free radicals, so that the possibility of fire flashover is reduced. The fire extinguishing agent absorbs heat generated by electrochemical reaction to reduce the temperature of a position to be subjected to flashover, so that the flashover phenomenon is eliminated, the probability of battery ignition or explosion is reduced, and the safety of the battery is effectively improved. Because the shell with the high-safety structure can cover the inhibitor, the flame retardant and the fire extinguishing agent inside, liquid cannot seep into the electrolyte when the battery works normally, and the performances of the battery such as multiplying power, circulation and the like cannot be influenced. When the temperature in the battery cell module rises to the melting point of the high-safety structure shell, the inhibitor, the flame retardant and the fire extinguishing agent are gradually released, so that the thermal runaway phenomenon is suppressed stage by stage, and the safety performance is improved.
Optionally, the housing of the high-safety structure has a first molten state, a second molten state, and a third molten state. The temperature of the electrolyte reaches T1In the process, the high-safety shell is melted to a first molten state, and the inhibitor is released from the high-safety shell. The temperature of the electrolyte reaches T2When the high-safety structure shell is melted to the second melting state, the flame retardant is released from the high-safety structure shell. The temperature of the electrolyte reaches T3When the fire extinguishing agent is released from the shell of the high-safety structure, the shell of the high-safety structure is melted to a third molten state. Let the self-heat-release initiation temperature of the battery be Th0Then T ish0＜T1＜T2＜T3＜Th1. The battery is in a normal working state when the battery does not start to release heat, at the moment, the shell of the high-safety structure tightly covers the internal inhibitor, the flame retardant and the fire extinguishing agent, so that the phenomenon that liquid leaks in electrolyte to influence the movement of lithium ions between a positive electrode and a negative electrode is avoided, and the battery is ensured to have high specific discharge capacity. T1 and T2And T3Are all less than the thermal runaway initiation temperature Th1The battery can release the inhibitor, the flame retardant and the fire extinguishing agent before reaching the temperature at which the battery can possibly cause thermal runaway, the heat production speed in the battery is slowed down, and the occurrence of the thermal runaway is effectively inhibited.
Alternatively, the inhibitors include Dibenzylamine (DBA), Benzylamine (BA), and Trihexylamine (THA). Dibenzylamine, benzylamine and trihexylamine are effective retardants for thermal runaway of lithium ion batteries, and dibenzylamine can react with a fully charged positive electrode to form a solid-electrolyte membrane on the surface of the positive electrode, so that the impedance of charge exchange is increased, namely, the charge transfer resistance is increased. The dibenzylamine and the benzylamine can greatly reduce the conductivity of the electrolyte, reduce the transference number of lithium ions in the electrolyte, and inhibit the lithium ions from transferring between a positive electrode and a negative electrode, so that the heat generation is reduced. Trihexylamine is highly wetting to the solid-electrolyte separator and immiscible with the electrolyte, so it can hinder lithium ion transport, and a certain concentration of trihexylamine can reduce the peak temperature by 50%.
Optionally, the flame retardant comprises trimethyl phosphate (TMP) and/or triphenyl phosphate (TPP). Trimethyl phosphate and triphenyl phosphate have the characteristics of high flame retardance, low pollution, electrochemical stability and the like. The working principle is free radical scavenging reaction, and when the temperature of the battery rises too fast, phosphorus-containing molecules are thermally decomposed to generate phosphorus-containing free radicals. The phosphorus-containing radicals can scavenge hydrogen and hydroxyl active radicals generated by side reactions to reduce the possibility of a flash fire, thereby preventing fire and explosion. Trimethyl phosphate and triphenyl phosphate have strong capability of decomposing phosphorus-containing free radicals, and the content of the free radicals with the flame-retardant function in gas phase is high, so that the flame-retardant effect is effectively improved. The flame retardant may also include fluorinated phosphites, fluorinated phosphates, and the like.
Optionally, the fire extinguishing agent includes perfluorohexanone. The perfluorohexanone is easy to vaporize and exists in a gaseous state, and can rapidly absorb heat to achieve the effect of extinguishing fire.
In this embodiment, a lithium nickel cobalt manganese oxide ternary 8-series battery is selected to verify the improvement effect of the high-safety structure on thermal runaway. The positive electrode of the lithium ion battery is prepared from an NCM811 polycrystalline material (the content ratio of nickel, cobalt and manganese is 0.8: 0.1: 0.1), CNT slurry, carbon black and polyvinylidene fluoride in a weight ratio of 82: 15: 0.5: 1.0: 1.5. the compacted density of the positive plate is 3.5g/cm3. The proportion of graphite, carbon black, sodium carboxymethyl cellulose and Styrene Butadiene Rubber (SBR) binder in the negative electrode is 95.5: 0.8: 1.2: 2.5. the compacted density of the negative plate is 1.60g/cm3. The solvent of the electrolyte injected into the battery cell module comprises Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) and dimethyl carbonate (DMC), and the ratio EC of several lipid solvents is as follows: EMC: DEC: DMC is 5: 2: 1.5: 1.5. the electrolyte is prepared by mixing at least two of LIPF6, LIFSI, LiBOB, LiODFB, LiFSI, LiTFSI and LiPO2F2, and the solubility is 1.0mol/L-1.2 mol/L. The working voltage of the battery is 2.8V-4.2V. When the high safety structure is not installed on the naked electric core, the thermal runaway experiment test result of the battery is as follows: self-exothermic onset temperature Th0At 76.668 ℃ C, a thermal runaway initiation temperature Th1At 134.699 ℃ C, the maximum temperature T of thermal runawayhmaxThe temperature was 347.100 ℃.
In this embodiment, the housing of the high security structure comprises a polymerOne or more of ethylene wax, polyethylene, polyurethane, polyamide resin, polysulfide rubber, phenolic resin, epoxy resin, ethylene resin and silicon resin. That is, the housing of the high-safety structure is a plastic comprising one or more of the above-mentioned compounds, and has a melting point M0。
The plastic high-safety structure shell prepared from the compound has a lower melting point, and can be ensured to enter a molten state before the thermal runaway initiation temperature, so that an inhibitor, a flame retardant and a fire extinguishing agent are gradually released, an exothermic reaction is inhibited, and the temperature rise is slowed down. And this high safe structure casing has stronger corrosion resistance, can resist the strong corrosivity of electrolyte, ensures that the battery normally works the casing can not be corroded and damaged, prevents that inside inhibitor, fire retardant and the fire extinguishing agent from spilling over and leading to the electrolyte performance to descend when the battery normally works. In addition, the plastic high-safety structure shell is light in weight and easy to reduce the weight of the whole battery.
In the thermal runaway test in this example, the percentage of dibenzylamine, benzylamine, and trihexylamine in the inhibitor was 50% to 70%, 15% to 25%, and 15% to 25%. Trimethyl phosphate is adopted as the flame retardant. The fire extinguishing agent adopts perfluorohexanone. The ratio of the inhibitor, the flame retardant and the fire extinguishing agent is 0.6: 0.2: 0.2, total amount is 200 ml. Through effective experiments for many times, the lithium battery selected in the embodiment has the following thermal runaway experimental result after being implanted into a high-safety structure: self-exothermic onset temperature Th0At 76.890 ℃ C, a thermal runaway initiation temperature Th1At 141.982 ℃ C, the maximum temperature T of thermal runawayhmaxThe temperature was 310.306 ℃.
Thermal runaway induced temperature T compared with a battery without an implanted high-safety structureh1A significant increase, i.e. an increase in the minimum temperature threshold that may cause thermal runaway. That is to say, when the high safety structure is not implanted, thermal runaway may occur when the internal temperature of the cell module reaches 134.699 ℃, and after the high safety structure is implanted, thermal runaway may be caused when the internal temperature of the cell module reaches 141.982 ℃, so that the temperature range of the safe operation of the battery is expanded. In addition, the maximum temperature T of thermal runawayhmaxIs significantly reduced, i.e.The highest temperature value which can be reached by the battery is reduced, and the possibility of fire or explosion of the battery is reduced to a certain extent.
The embodiment also provides a battery which is manufactured by adopting the preparation method of the high-safety battery, and comprises a plurality of battery cell modules and a plurality of high-safety structures. Naked electric core all is provided with in the casing of every electric core module to it has electrolyte to fill. The high-safety structure is arranged on the naked electric core and is soaked in the electrolyte. The housing of the high security configuration defines a reservoir chamber. The liquid storage cavity is internally stored with an inhibitor, a fire retardant and a fire extinguishing agent. The melting point of the case of the high safety structure is lower than the thermal runaway initiation temperature T of the batteryh1And the inhibitor, the fire retardant and the fire extinguishing agent are sequentially released into the electrolyte along with the increase of the temperature in the electric core module.
In the battery that this embodiment provided, all be provided with high safety structure on the naked electric core of every electric core module, because the casing of high safety structure can wrap up inside inhibitor, fire retardant and fire extinguishing agent, the battery is normal during operation, liquid can not ooze to in the electrolyte, consequently can not influence the multiplying power of battery, performance such as circulation, when the temperature risees to the melting point of high safety structure casing in the electric core module, inhibitor, fire retardant and fire extinguishing agent release gradually, in order to suppress thermal runaway phenomenon stage by stage, promote the security performance.
Example two
The present embodiment provides a method for preparing a high-safety battery, which is different from the first embodiment in that:
optionally, two high-safety structures are installed on the same bare cell. One of the high-safety structure shells is an alloy safety shell, and the other high-safety structure shell is a polymer safety shell. The alloy safety shell comprises one or more of bismuth element, lead element, tin element and cadmium element, and the polymer safety shell comprises one or more of polyethylene wax, polyethylene, polyurethane, polyamide resin, polysulfide rubber, phenolic resin, epoxy resin, vinyl resin and silicon resin.
The alloy containing bismuth, lead, tin and cadmium has the characteristics of low melting point and high corrosion resistance, so that the shell of the high-safety structure can enter a molten state before the temperature is initiated by thermal runaway, and therefore the inhibitor, the flame retardant and the fire extinguishing agent are gradually released, the exothermic reaction is inhibited, and the temperature rise is slowed down. Meanwhile, the alloy safety shell has a good protection effect when the battery works normally, can resist the strong corrosion of electrolyte, avoids the shell from being corroded and damaged, and prevents the inhibitor, the fire retardant and the fire extinguishing agent inside from leaking in the electrolyte.
The alloy safety shell and the polymer safety shell both have the excellent characteristics of low melting point and high corrosion resistance, and can timely and effectively inhibit the exothermic reaction in the electric core module on the premise of ensuring high energy density when the battery works normally, slow down the temperature rise speed, and avoid the battery from being ignited and even exploded due to thermal runaway.
In this embodiment, the melting point of the alloy safety shell is M1The melting point of the polymeric safety shell is M2，M1≠M2≠M0That is, the melting point of the alloy safety case and the melting point of the polymer safety case in the second embodiment are different from the melting point of the case of the high safety structure in the first embodiment. By arranging two high-safety structures with different melting points of the shell, the inhibitor, the fire retardant and the fire extinguishing agent can be ensured to be gradually released after the temperature in the electric core module reaches a certain temperature, and the reliability is improved. In addition, the layering of the release of the inhibitor, the flame retardant and the fire extinguishing agent can be improved, and for example, M is used1Less than M2If above M1The flame retardant released at the temperature can not completely eliminate inflammable free radicals generated by electrochemical reaction in the electrolyte, and the content of the flame retardant is higher than M2The flame retardant released at the temperature can further eliminate inflammable free radicals, and the thermal runaway inhibition effect is improved.
In this embodiment, the same nickel cobalt lithium manganate ternary 8-series battery as in the first embodiment is selected to verify the improvement effect of the high safety structure on thermal runaway, and specific parameters of the lithium ion battery and the thermal runaway experimental results when the high safety structure is not implanted are shown in the first embodiment.
In the thermal runaway test in this example, two of the inhibitors10-15% of benzylamine, 10-15% of benzylamine and 70-80% of trihexylamine. Triphenyl phosphate is used as the flame retardant. The fire extinguishing agent adopts perfluorohexanone. The ratio of the inhibitor, the flame retardant and the fire extinguishing agent is 0.5: 0.4: 0.1, and the total amount is 200 ml. Through effective experiments for many times, the lithium battery selected in the embodiment has the following thermal runaway experimental result after being implanted into a high-safety structure: self-exothermic onset temperature Th0At 75.692 ℃ C, a thermal runaway initiation temperature Th1At 143.670 ℃ C, the maximum temperature T of thermal runawayhmaxThe temperature was 301.600 ℃.
It is apparent that the thermal runaway initiation temperature T is comparable to that of a battery not implanted with a high safety structureh1A significant increase, i.e. an increase in the minimum temperature threshold that may cause thermal runaway. That is to say, when the high safety structure is not implanted, thermal runaway may occur when the internal temperature of the cell module reaches 134.699 ℃, and after the high safety structure is implanted, thermal runaway may be caused when the internal temperature of the cell module reaches 143.670 ℃, so that the temperature range of the safe operation of the battery is expanded. In addition, the maximum temperature T of thermal runawayhmaxThe temperature is obviously reduced (from 347.100 ℃ to 301.600 ℃), namely the highest temperature value which can be reached by the battery is reduced, and the effect is obvious.
Optionally, in this embodiment, the interposer in the cell module is an alloy interposer made of one or more of bismuth, lead, tin, cadmium, and the like, and is used to replace one of the housings with a high safety structure, that is, the alloy safety housing described above. The alloy adapter plate is provided with a liquid storage cavity, and three immiscible liquids of an inhibitor, a fire retardant and a fire extinguishing agent are stored in the liquid storage cavity. The lower plastic part in the cell module is made of one or more of polyethylene wax, polyethylene, polyurethane, polyamide resin, polysulfide rubber, phenolic resin, epoxy resin, vinyl resin, silicone resin and the like, and is used for replacing another shell with a high-safety structure, namely the polymer safety shell. The lower plastic part is also provided with a liquid storage cavity, and three mutually immiscible liquids of an inhibitor, a fire retardant and a fire extinguishing agent are stored in the liquid storage cavity.
Use the adaptor piece and replace the casing of two high safety structure with lower plastic part in this embodiment, can reduce the inside part quantity of electric core module, reduce the material quantity, save the resource, do benefit to the environmental protection, and can reduce the whole volume of battery, do benefit to the miniaturization of devices such as cell-phone, car.
EXAMPLE III
The present embodiment provides a method for preparing a high-safety battery, which is different from the first embodiment in that:
optionally, two high-safety structures are installed on the same bare cell. One of the high-safety structure shells is an alloy safety shell, and the other high-safety structure shell is a polymer safety shell. The alloy safety shell comprises one or more of bismuth element, lead element, tin element and cadmium element, and the polymer safety shell comprises one or more of polyethylene wax, polyethylene, polyurethane, polyamide resin, polysulfide rubber, phenolic resin, epoxy resin, vinyl resin and silicon resin. The alloy safety shell and the polymer safety shell both have the excellent characteristics of low melting point and high corrosion resistance, and can timely and effectively inhibit the exothermic reaction in the electric core module on the premise of ensuring high energy density when the battery works normally, slow down the temperature rise speed, and avoid the battery from being ignited and even exploded due to thermal runaway.
In this embodiment, the melting point of the alloy safety shell is M3Said polymeric safety shell having a melting point M4，M3≠M4≠M1≠M2That is, the melting point of the alloy safety case and the melting point of the polymer safety case in the third embodiment are different from the melting point of the alloy safety case and the melting point of the polymer safety case in the second embodiment.
In this embodiment, the same nickel cobalt lithium manganate ternary 8-series battery as in the first embodiment is selected to verify the improvement effect of the high safety structure on thermal runaway, and specific parameters of the lithium ion battery and the thermal runaway experimental results when the high safety structure is not implanted are shown in the first embodiment.
In the thermal runaway test in this example, the percentage of dibenzylamine in the inhibitor was 10% to 15%, the percentage of benzylamine was 10% to 15%, and the percentage of trihexylamine wasThe proportion is 70-80%. Triphenyl phosphate is used as the flame retardant. The fire extinguishing agent adopts perfluorohexanone. The ratio of the inhibitor, the flame retardant and the fire extinguishing agent is 0.3: 0.3: 0.4, the total amount is 200 ml. Through effective experiments for many times, the lithium battery selected in the embodiment has the following thermal runaway experimental result after being implanted into a high-safety structure: self-exothermic onset temperature Th0At 76.692 ℃ C, a thermal runaway initiation temperature Th1At 136.670 ℃ C, the maximum temperature T of thermal runawayhmaxThe temperature was 321.062 ℃.
Thermal runaway induced temperature T compared with a battery without an implanted high-safety structureh1An increase is obtained, i.e. an increase in the minimum temperature threshold at which thermal runaway may occur. Maximum temperature of thermal runaway ThmaxThe temperature is obviously reduced (from 347.100 ℃ to 321.062 ℃), namely the highest temperature value which can be reached by the battery is reduced.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Numerous obvious variations, adaptations and substitutions will occur to those skilled in the art without departing from the scope of the invention. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a high-safety battery is characterized by comprising the following steps:
manufacturing a shell with a high safety structure: the melting point of the casing of the high-safety structure is lower than the thermal runaway initiation temperature T of the batteryh1；
Injecting an inhibitor, a fire retardant and a fire extinguishing agent into the high safety structure housing: the inhibitor is used for inhibiting the movement of lithium ions in the electrolyte, the fire retardant is used for removing inflammable free radicals generated by electrochemical reaction in the electrolyte, the fire extinguishing agent is used for absorbing heat generated by the electrochemical reaction, and the inhibitor, the fire retardant and the fire extinguishing agent are mutually immiscible;
assembling the battery cell module: installing a naked electric core in a shell of the electric core module, installing the high-safety structure in the naked electric core, injecting electrolyte into the shell of the electric core module and packaging the electric core module;
and assembling the circuit board and the plurality of battery cell modules to form the high-safety battery.
2. The method for manufacturing a high-safety battery according to claim 1, wherein the case of the high-safety structure has a first molten state, a second molten state, and a third molten state, and the self-exothermic initiation temperature of the battery is Th0；
The temperature of the electrolyte reaches T1When the high-safety structure shell is melted to a first molten state, the inhibitor is released from the high-safety structure shell;
the temperature of the electrolyte reaches T2When the high-safety structure shell is melted to a second molten state, the flame retardant is released from the high-safety structure shell;
the temperature of the electrolyte reaches T3When the fire extinguishing agent is released from the shell of the high-safety structure, the shell of the high-safety structure is melted to a third molten state;
Th0＜T1＜T2＜T3＜Th1。
3. the method for manufacturing a high-safety battery according to claim 1, wherein the inhibitor includes Dibenzylamine (DBA), Benzylamine (BA), and Trihexylamine (THA), the flame retardant includes trimethyl phosphate (TMP) and/or triphenyl phosphate (TPP), and the fire extinguishing agent includes perfluorohexanone.
4. The method of claim 3, wherein the housing of the high-safety structure comprises one or more of polyethylene wax, polyethylene, polyurethane, polyamide resin, polysulfide rubber, phenolic resin, epoxy resin, vinyl resin, and silicone resin.
5. The method for preparing a high-safety battery according to claim 4, wherein the inhibitor comprises 50 to 70% of dibenzylamine, 15 to 25% of benzylamine, and 15 to 25% of trihexylamine, wherein trimethyl phosphate is used as the flame retardant, and wherein the ratio of the inhibitor, the flame retardant, and the fire extinguishing agent is 0.6: 0.2: 0.2.
6. the method for manufacturing a high-safety battery according to claim 3, wherein two high-safety structures are manufactured and mounted on the same bare cell, wherein the shell of one high-safety structure is an alloy safety shell, the shell of the other high-safety structure is a polymer safety shell, the alloy safety shell comprises one or more of bismuth, lead, tin and cadmium, and the polymer safety shell comprises one or more of polyethylene wax, polyethylene, polyurethane, polyamide resin, polysulfide rubber, phenolic resin, epoxy resin, vinyl resin and silicone resin.
7. The method for preparing a high-safety battery according to claim 6, wherein the alloy safety case has a melting point of M1Said polymeric safety shell having a melting point M2，M1≠M2In the inhibitor, the percentage of dibenzylamine is 10% -15%, the percentage of benzylamine is 10% -15%, and the percentage of trihexylamine is 70% -80%, the flame retardant is triphenyl phosphate, and the ratio of the inhibitor, the flame retardant and the fire extinguishing agent is 0.5: 0.4: 0.1.
8. the method for preparing a high-safety battery according to claim 6, wherein the alloy safety case has a melting point of M3Said polymeric safety shell having a melting point M4，M3≠M4The percentage of dibenzylamine in the inhibitor is 10 to 15 percent, 10 to 15 percent of benzylamine and 70 to 80 percent of trihexylamine, wherein the flame retardant is triphenyl phosphate, and the ratio of the inhibitor to the flame retardant to the fire extinguishing agent is 0.3: 0.3: 0.4.
9. the method of claim 6, wherein the alloy safety housing comprises an interposer within the electrical core module and the polymer safety housing comprises a lower plastic within the electrical core module.
10. A battery manufactured by the method for manufacturing a high safety battery according to any one of claims 1 to 9, comprising:
the battery cell module comprises a plurality of battery cell modules, wherein a naked battery cell is arranged in a shell of each battery cell module and is filled with electrolyte;
the high-safety structure is arranged in the naked electric core and soaked in the electrolyte, a shell of the high-safety structure defines a liquid storage cavity, an inhibitor, a fire retardant and a fire extinguishing agent are stored in the liquid storage cavity, and the melting point of the shell of the high-safety structure is lower than the thermal runaway initiation temperature T of the batteryh1The inhibitor, the fire retardant and the fire extinguishing agent are sequentially released into the electrolyte as the temperature in the electric core module increases.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110990157.3A CN113707971B (en) | 2021-08-26 | 2021-08-26 | Preparation method of high-safety battery and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110990157.3A CN113707971B (en) | 2021-08-26 | 2021-08-26 | Preparation method of high-safety battery and battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113707971A true CN113707971A (en) | 2021-11-26 |
| CN113707971B CN113707971B (en) | 2023-05-09 |
Family
ID=78655432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110990157.3A Active CN113707971B (en) | 2021-08-26 | 2021-08-26 | Preparation method of high-safety battery and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113707971B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114699678A (en) * | 2022-03-30 | 2022-07-05 | 清华大学 | Miniature fire extinguishing device and fire extinguishing method of lithium ion battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103825059A (en) * | 2014-02-13 | 2014-05-28 | 浙江吉利控股集团有限公司 | Heat management and automatic-fire extinguishing system for vehicle battery |
| CN105742728A (en) * | 2014-12-09 | 2016-07-06 | 北京有色金属研究总院 | Lithium-ion secondary battery |
| CN109568833A (en) * | 2019-01-10 | 2019-04-05 | 华南理工大学 | A kind of anti-re-ignition automatic fire extinguisher of power battery pack and method |
| CN110433419A (en) * | 2019-06-28 | 2019-11-12 | 浙江南都电源动力股份有限公司 | Lithium electric heating uncontrolled fire inhibits capsule and lithium ion battery |
| KR20200061814A (en) * | 2018-11-26 | 2020-06-03 | (주)비에이에너지 | Device for fire extinguishing |
| CN112029343A (en) * | 2020-07-17 | 2020-12-04 | 清华大学 | Coating, positive plate, negative plate, diaphragm and lithium ion battery for inhibiting thermal runaway of lithium ion battery |
-
2021
- 2021-08-26 CN CN202110990157.3A patent/CN113707971B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103825059A (en) * | 2014-02-13 | 2014-05-28 | 浙江吉利控股集团有限公司 | Heat management and automatic-fire extinguishing system for vehicle battery |
| CN105742728A (en) * | 2014-12-09 | 2016-07-06 | 北京有色金属研究总院 | Lithium-ion secondary battery |
| KR20200061814A (en) * | 2018-11-26 | 2020-06-03 | (주)비에이에너지 | Device for fire extinguishing |
| CN109568833A (en) * | 2019-01-10 | 2019-04-05 | 华南理工大学 | A kind of anti-re-ignition automatic fire extinguisher of power battery pack and method |
| CN110433419A (en) * | 2019-06-28 | 2019-11-12 | 浙江南都电源动力股份有限公司 | Lithium electric heating uncontrolled fire inhibits capsule and lithium ion battery |
| CN112029343A (en) * | 2020-07-17 | 2020-12-04 | 清华大学 | Coating, positive plate, negative plate, diaphragm and lithium ion battery for inhibiting thermal runaway of lithium ion battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114699678A (en) * | 2022-03-30 | 2022-07-05 | 清华大学 | Miniature fire extinguishing device and fire extinguishing method of lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113707971B (en) | 2023-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5145367B2 (en) | Non-aqueous electrolyte and lithium secondary battery using the same | |
| US7553588B2 (en) | Non-aqueous electrolyte and a lithium secondary battery comprising the same | |
| KR101073228B1 (en) | Nonaqueous Electrolyte Secondary Battery | |
| US7968234B2 (en) | Non-aqueous electrolyte and lithium secondary battery comprising same | |
| KR101376414B1 (en) | Solvent for dissolution of electrolytic salt of lithium secondary battery | |
| JP5708244B2 (en) | Non-aqueous electrolyte and lithium ion secondary battery using the same | |
| EP2166610A1 (en) | Electrolyte for lithium ion secondary battery and lithium ion secondary battery comprising the same | |
| CN100466365C (en) | High safety, high power lithium ion power battery | |
| JP5983370B2 (en) | Lithium ion secondary battery, secondary battery system using the same, and non-aqueous electrolyte for lithium ion secondary battery | |
| KR20060014280A (en) | Non-aqueous electrolyte for secondary batteries and secondary batteries containing the same | |
| JP5421853B2 (en) | Non-aqueous electrolyte and lithium secondary battery using the same | |
| JP5942892B2 (en) | Non-aqueous electrolyte, non-aqueous electrolyte secondary battery using the same, and secondary battery system using the non-aqueous electrolyte secondary battery | |
| Guo et al. | The causes of fire and explosion of lithium ion battery for energy storage | |
| JP4765629B2 (en) | Non-aqueous electrolyte and lithium secondary battery | |
| WO2020063885A1 (en) | Non-aqueous electrolyte, lithium ion battery, battery module, battery pack and apparatus | |
| CN113707971B (en) | Preparation method of high-safety battery and battery | |
| CN108666524B (en) | Battery electrode, preparation method thereof and lithium ion battery | |
| JP5966896B2 (en) | Lithium ion secondary battery, secondary battery system using the same, and non-aqueous electrolyte for lithium ion secondary battery | |
| CN107507998B (en) | Overcharge-resistant method for non-aqueous electrolyte secondary battery | |
| WO2012063286A1 (en) | Secondary battery | |
| CN108054430B (en) | Lithium ion battery electrolyte and lithium ion battery | |
| WO2020063889A1 (en) | Non-aqueous electrolyte, lithium ion battery, battery module, battery pack and device | |
| KR100703845B1 (en) | Non-aqueous electrolyte for Lithium Secondary Batteries and Lithium Secondary Batteries containing the same | |
| KR100923334B1 (en) | Nonaqueous electrolyte for rechargeable lithium battery and rechargeable lithium battery the same | |
| KR100693288B1 (en) | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
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 |