CN1698231A - Lithium secondary battery and nonaqueous electrolyte - Google Patents
Lithium secondary battery and nonaqueous electrolyte Download PDFInfo
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- CN1698231A CN1698231A CNA018200052A CN01820005A CN1698231A CN 1698231 A CN1698231 A CN 1698231A CN A018200052 A CNA018200052 A CN A018200052A CN 01820005 A CN01820005 A CN 01820005A CN 1698231 A CN1698231 A CN 1698231A
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- CN
- China
- Prior art keywords
- lithium
- secondary battery
- electrolytic solution
- organic compound
- nonaqueous electrolytic
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 106
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000011255 nonaqueous electrolyte Substances 0.000 title abstract 2
- 239000003792 electrolyte Substances 0.000 claims abstract description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 45
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 45
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 22
- 239000010941 cobalt Substances 0.000 claims abstract description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 150000004997 alkyl benzene derivatives Chemical group 0.000 claims abstract description 12
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 10
- 239000001989 lithium alloy Substances 0.000 claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 8
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical group CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 30
- 230000001590 oxidative effect Effects 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical group [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 15
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 150000002641 lithium Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 3
- 230000020169 heat generation Effects 0.000 abstract 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 32
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 24
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 23
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 21
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 19
- 229910013870 LiPF 6 Inorganic materials 0.000 description 18
- 239000004305 biphenyl Substances 0.000 description 16
- 235000010290 biphenyl Nutrition 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 230000004087 circulation Effects 0.000 description 11
- -1 3-R-thiophene Chemical compound 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- QUBJDMPBDURTJT-UHFFFAOYSA-N 3-chlorothiophene Chemical compound ClC=1C=CSC=1 QUBJDMPBDURTJT-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
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- 239000011230 binding agent Substances 0.000 description 4
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- 238000002156 mixing Methods 0.000 description 4
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- VIPWUFMFHBIKQI-UHFFFAOYSA-N 1-fluoro-4-methoxybenzene Chemical compound COC1=CC=C(F)C=C1 VIPWUFMFHBIKQI-UHFFFAOYSA-N 0.000 description 2
- GSFNQBFZFXUTBN-UHFFFAOYSA-N 2-chlorothiophene Chemical compound ClC1=CC=CS1 GSFNQBFZFXUTBN-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WIXDSJRJFDWTNY-UHFFFAOYSA-N 1,3-ditert-butyl-5-methylbenzene Chemical compound CC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 WIXDSJRJFDWTNY-UHFFFAOYSA-N 0.000 description 1
- HTICYVWLHLMMPF-UHFFFAOYSA-N 1-methyl-4-(2-methylbutan-2-yl)benzene Chemical compound CCC(C)(C)C1=CC=C(C)C=C1 HTICYVWLHLMMPF-UHFFFAOYSA-N 0.000 description 1
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 description 1
- VUAXHMVRKOTJKP-UHFFFAOYSA-M 2,2-dimethylbutanoate Chemical compound CCC(C)(C)C([O-])=O VUAXHMVRKOTJKP-UHFFFAOYSA-M 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- DWSYCKRMYCWSQT-UHFFFAOYSA-N 5-butan-2-yl-5-ethylcyclohexa-1,3-diene Chemical compound CCC(C)C1(CC)CC=CC=C1 DWSYCKRMYCWSQT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013375 LiC Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000009783 overcharge test Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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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
- H01M10/056—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
Rapid heat generation that is likely to occur at the time of overcharge can be effectively prevented by adding certain organic compounds (e.g., tertiary alkylbenzene derivatives) to a nonaqueous electrolytic solution for a lithium secondary battery composed of a positive electrode composed of a composite metal oxide of lithium and cobalt or a composite metal oxide of lithium and nickel, a negative electrode, and a nonaqueous electrolytic solution; the negative electrode is made of lithium metal, a lithium alloy, or a material capable of occluding and releasing lithium; the nonaqueous electrolyte is formed by dissolving an electrolyte in a nonaqueous solvent; the organic compound is decomposed when the lithium secondary battery is overcharged, and cobalt or nickel in the positive electrode is eluted and deposited on the negative electrode by the action of the decomposition product.
Description
Technical field
The present invention relates to lithium secondary battery and can be advantageously used in nonaqueous electrolytic solution in the lithium secondary battery.The battery behavior that the invention particularly relates to cycle characteristics, capacitance, preservation characteristics etc. is good, and have and to suppress because the lithium secondary battery of the fail safe of the caused rapid heating that overcharges of lithium secondary battery, and can be advantageously used in the nonaqueous electrolytic solution of this class lithium secondary battery.
Background technology
In recent years, lithium secondary battery is used by the driving power as miniaturized electronics etc. widely.In addition, lithium secondary battery not only can be used for portable electronic commnication devices such as miniature camera, mobile phone, notebook personal computer, and very hopeful power supply use as automobile.This lithium secondary battery mainly is made of positive pole, nonaqueous electrolytic solution and negative pole, uses by LiCoO in the ordinary course of things
2Deng the composite oxides of lithium as positive pole with carbonaceous material or lithium metal lithium secondary battery as negative pole.In addition, as the nonaqueous solvents of this electrolyte for lithium secondary batteries, generally use the carbonates of ethylene carbonate (EC), propylene carbonate (PC) etc.
For this class lithium secondary battery, when surpassing the overcharging of common operating voltage, can emit superfluous lithium from positive pole, on negative pole, separate out superfluous lithium simultaneously, thereby generate dendrite.So make positive and negative the two poles of the earth that the instabilityization of chemistry take place.When in a single day positive and negative the two poles of the earth become chemically unstable, will soon react with the carbonates in the nonaqueous electrolytic solution, decompose, thereby cause fierce exothermic reaction.Therefore cause all heatings singularly of battery, thereby produce the problem of infringement battery security.The energy density of lithium secondary battery is high more, and this situation is just serious more.
In order to solve such problem, for example open and proposed a small amount of aromatic compounds of interpolation in electrolyte in the flat 7-302614 communique, so that guarantee for the fail safe that overcharges as additive the spy.Open in the flat 7-302614 communique this spy, use molecular weight below 500 and have the additive of the anisole derivative etc. of pi-electron track as electrolyte, this class anisole derivative has the invertibity oxidation-reduction potential in the also high current potential zone of anodal current potential when completely charging.Because this class anisole derivative has back and forth (redox shuttle) effect of redox in battery, therefore can guarantee the fail safe of battery when overcharging.
Te Kaiping 9-106835 communique has proposed a kind of method that can guarantee battery security when overcharging, this method is to use carbonaceous material to use biphenyl, 3-R-thiophene, 3-chlorothiophene, the furans additive as electrolyte as negative pole and by about 1～4% concentration, when voltage surpasses the maximum working voltage of battery, owing to the polymerization of biphenyl makes the internal resistance increase of battery, thereby can when overcharging, guarantee the fail safe of battery.
Te Kaiping 9-171840 communique has also proposed a kind of method of guaranteeing battery security when overcharging, this method is used biphenyl, 3-R-thiophene, 3-chlorothiophene, furans equally, when battery arrives the voltage that surpasses its maximum working voltage, owing to generation polymerizations such as biphenyl produce gas, so just make the action of internal current shearing device, internal short-circuit takes place, and therefore can guarantee the safety of battery when overcharging.
Te Kaiping 10-321258 communique has also proposed a kind of method of guaranteeing cell safety when overcharging, this method is used biphenyl, 3-R-thiophene, 3-chlorothiophene, furans equally, when battery arrives the voltage that surpasses its maximum working voltage, owing to the polymerization of biphenyl etc. produces electric conductive polymer, internal short-circuit takes place, and therefore can guarantee the safety of battery when overcharging.
2, polymerization just takes place in 2-diphenyl propane etc., thereby produces gas, makes the action of internal current shearing device, perhaps generates electric conductive polymer, causes taking place internal short-circuit, thereby can guarantee the fail safe of battery when overcharging.
Yet, when overcharging, can work effectively owing to the redox inhibitory action though open the anisole derivative that suggestion is used in the flat 7-302614 communique the spy, its exists brings dysgenic problem for cycle characteristics or preservation characteristics.Promptly, when the anisole derivative of putting down in writing in this communique uses under the condition of high temperature more than 40 ℃ or common operating voltage, if be subjected to the effect of high slightly voltage partly, will be along with the carrying out that discharges and recharges, make anisole slowly decompose, thereby cause intrinsic battery behavior to reduce, this is the problem that exists.Therefore, because the anisole derivative decomposes lentamente along with common discharging and recharging, thereby cause its content to reduce gradually, so after the test that overcharges of having carried out 300 circulations, just can not fully guarantee the safety of battery.
In addition, opening flat 9-106835 communique, spy the spy opens biphenyl, 3-R-thiophene, 3-chlorothiophene, the furans that suggestion is used in flat 9-171840 communique and the flat 10-321258 communique of Te Kai and works effectively when overcharging similarly, but as above-mentioned spy open point out in the flat 11-162512 communique, above-mentioned additive can produce harmful effect to the cycle characteristics and the preservation characteristics of battery, and this harmful effect becomes more remarkable along with the increase of biphenyl addition, and this is the problem that exists.This be because, the oxidized decomposition of current potential meeting below 4.5V such as biphenyl, therefore, when using at the high temperature more than 40 ℃ or under common operating voltage, as long as occur high slightly voltage partly, biphenyl etc. will decompose at leisure, thus the time its content reduce gradually, therefore cause the cycle life of battery to reduce.And then, biphenyl etc. is slowly decomposed and therefore its content is reduced gradually, so after the test that overcharges of carrying out 300 circulations, just often can not fully guarantee the safety of battery.
Open the interpolation of putting down in writing in the flat 11-162512 communique 2 the spy, though the battery of 2-diphenyl propane do not resemble add biphenyl battery when overcharging good fail safe, but when comparing with the battery that does not add any additives, it still is good to the fail safe that overcharges.On the other hand, add 2, though the battery of 2-diphenyl propane can obtain to compare with the battery that does not add any additives than the better cycle characteristics of battery that adds biphenyl, its cycle characteristics is inferior.Therefore, according to above-mentioned communique record, in order to obtain to sacrifice the fail safe of a part than the better cycle characteristics of battery that adds biphenyl.That is to say, may not successfully take into account simultaneously and guarantee battery behavior and this two aspect of fail safe that prevents to overcharge etc.
Main purpose of the present invention is to solve the above-mentioned problem relevant with electrolyte for lithium secondary batteries, provide a kind of have can prevent because all good lithium secondary battery of battery behavior of the fail safe of the caused rapid heating that overcharges of battery etc., cycle characteristics, capacitance, preservation characteristics etc.
Summary of the invention
The present invention relates to a kind of method that is used to suppress the rapid heating that lithium secondary battery causes when overcharging, this lithium secondary battery is made of anodal, negative pole and nonaqueous electrolytic solution; Wherein, positive pole is made of the composite metal oxide of lithium and cobalt or the composite metal oxide of lithium and nickel; Negative pole by lithium metal, lithium alloy or can occlusion, the material of emitting lithium constitutes; Nonaqueous electrolytic solution by electrolyte dissolution in nonaqueous solvents and constitute, it is characterized in that, be dissolved with organic compound in this nonaqueous electrolytic solution in advance, this organic compound decomposes when overcharging, owing to the effect of this decomposition product makes cobalt or the nickel stripping in the positive pole and separates out on negative pole.
In addition, the invention still further relates to a kind of lithium secondary battery, this lithium secondary battery is made of positive pole, negative pole and nonaqueous electrolytic solution; Wherein, positive pole is made of the composite metal oxide of lithium and cobalt or the composite metal oxide of lithium and nickel; Negative pole by lithium metal, lithium alloy or can occlusion, the material of emitting lithium constitutes; Nonaqueous electrolytic solution by electrolyte dissolution in nonaqueous solvents and constitute, it is characterized in that, this nonaqueous electrolytic solution contains organic compound, this organic compound can decompose when lithium secondary battery overcharges, owing to the effect of this decomposition product makes cobalt or the nickel stripping in the positive pole and separates out on negative pole.
In addition, the invention still further relates to a kind of lithium secondary battery, this lithium secondary battery is made of positive pole, negative pole and nonaqueous electrolytic solution; Wherein, positive pole is made of the composite metal oxide of lithium and cobalt or the composite metal oxide of lithium and nickel; Negative pole by lithium metal, lithium alloy or can occlusion, the material of emitting lithium constitutes; Nonaqueous electrolytic solution, is characterized in that in nonaqueous solvents and constitute by electrolyte dissolution, this nonaqueous electrolytic solution contain with respect to lithium have+4.6V～+ organic compound of oxidizing potential in the 5.0V scope.
In addition, the invention still further relates to a kind of nonaqueous electrolytic solution, this nonaqueous electrolytic solution can be advantageously used in the lithium secondary battery that is made of positive pole, negative pole and nonaqueous electrolytic solution, and wherein, positive pole is made of the composite metal oxide of lithium and cobalt or the composite metal oxide of lithium and nickel; Negative pole by lithium metal, lithium alloy or can occlusion, the material of emitting lithium constitutes; Nonaqueous electrolytic solution is made of in nonaqueous solvents electrolyte dissolution; It is characterized in that, this nonaqueous electrolytic solution contain with respect to lithium have+4.6V～+ organic compound of oxidizing potential in the 5.0V scope.
As mentioned above, up to now, become known for preventing that the rapid heating (being called thermal runaway) that causes owing to overcharging from having following several method so that guarantee the method for cell safety: the method for redox reciprocating is played near the current potential place 4.5V; Increase the method for inside battery resistance by the current potential generation polymerization below 4.5V; Make the action of internal current shearing device to produce internal short-circuit by producing gas, perhaps by producing the method that electric conductive polymer produces internal short-circuit.
On the other hand, about the mechanism that overcharges of preventing of the present invention, can think as follows: since the above-mentioned organic compound that in nonaqueous electrolytic solution, contains with respect to lithium for+4.6V～+ oxidation Decomposition takes place during the current potential of 5.0V, when overcharging, promote the stripping of cobalt in the positive pole or nickel and make cobalt or nickel is separated out on negative pole, thereby suppress to have separated out lithium metal on negative pole and the carbonate reaction in the nonaqueous electrolytic solution.
In addition, in the present invention, can think that according to circumstances, owing to cobalt or nickel are separated out at inside battery cause internal short-circuit on negative pole, thereby obtain to prevent the effect that overcharges, the result can infer, and so just can fully guarantee the fail safe of battery.
And then, the above-mentioned organic compound that in nonaqueous electrolytic solution, contains since its with respect to the oxidizing potential of lithium up to+4.6V～+ 5.0V, therefore, even discharging and recharging repeatedly under the high temperature more than 40 ℃ and under common operating voltage, make local voltage cross 4.2V, above-mentioned organic compound can not decompose yet.So just can provide a kind of being not only to prevent that the fail safe that battery overcharges is good, and the also good lithium secondary battery of battery behavior of cycle characteristics, capacitance, preservation characteristics etc.
The preferred plan that is used to carry out an invention
As the organic compound that in electrolyte of the present invention, contains, can enumerate following compound.In addition, each organic compound is shown in the parantheses with respect to the oxidizing potential (recording by the method for putting down in writing among the following embodiment) of lithium.
As above-mentioned organic compound, preferred use at least a in the tertiary alkyl benzene derivative, for example can enumerate: 2-methyl-2-phenylpropane (4.9V), 1-fluoro-4-2-methyl-2-phenylpropane (4.9V), 1-chloro-4-2-methyl-2-phenylpropane (4.9V), 1-bromo-4-2-methyl-2-phenylpropane (4.9V), 1-iodo-4-2-methyl-2-phenylpropane (4.9V), 5-tert-butyl group meta-xylene (4.6V), 4-t-butyltoluene (4.7V), 3,5-di-t-butyl toluene (4.8V), 1,3-two 2-methyl-2-phenylpropanes (4.9V), 1,4-two 2-methyl-2-phenylpropanes (4.9V), 1,3, the 2-methyl-2-phenylpropane derivative of 5-three 2-methyl-2-phenylpropanes (5.0V) etc.Also can enumerate in addition: tert-amyl benzene (4.8V), 1-methyl-4-tert-amyl benzene (4.7V), 5-tertiary pentyl meta-xylene (4.6V), 1-ethyl-1-(methyl-propyl) benzene (4.8V), (1,1-diethyl propyl group) benzene (4.8V), 1,3-two tert-amyl benzenes (4.7V), 1, the tertiary alkyl benzene derivative of 4-two tert-amyl benzenes (4.7V) etc.
In addition, as above-mentioned organic compound, can use cyclohexyl benzene (4.7V), particularly low for example replace oxidizing potential height such as above-mentioned 2-methyl-2-phenylpropane as the cyclohexyl benzene of 4.7V for example be the part of the organic compound of 4.8～5.0V by using oxidizing potential, can improve to prevent the effect that overcharges.Should illustrate, for example under the situation of a part that replaces 2-methyl-2-phenylpropane with cyclohexyl benzene, with respect to the weight of cyclohexyl benzene, the content of 2-methyl-2-phenylpropane is preferably at 4 times below the amount, more preferably in the scope of 0.3～3 times of amount, in the scope particularly preferably in 0.5～2.5 times of amount.As mentioned above, prevent the effect that overcharges by merge using at least two kinds different above-mentioned organic compound of oxidizing potential, can improving.But, so long as can be+4.6V with respect to lithium～+ the current potential generation oxidation Decomposition of 5.0V, thereby when overcharging, can promote the cobalt in the positive pole or the organic compound of nickel stripping, the present invention to these compounds just without any qualification.
If the content of the above-mentioned organic compound in the electrolyte is too much, then conductivity of electrolyte etc. can change, thereby cause battery performance to reduce, if the content of organic compound is very few, then can not obtain to prevent fully because the effect of the rapid heating that caused of overcharging, therefore, with respect to the weight of electrolyte, organic compound is preferably in the scope of 0.1～10 weight %, in the scope particularly preferably in 1～5 weight %.
As the nonaqueous solvents that is applicable among the present invention, for example can enumerate: the cyclic carbonates of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC) etc.; The lactone of gamma-butyrolacton etc.; The linear carbonate class of dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC) etc.; Oxolane, 2-methyltetrahydrofuran, 1,4-diox, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, 1, the ethers of 2-dibutoxy ethane etc.; The nitrile of acetonitrile etc.; The ester class of methyl propionate, methyl pivalate, neopentanoic acid monooctyl ester etc.; The amide-type of dimethyl formamide etc.
These nonaqueous solventss can use wherein a kind of, also it can be used in combination.Combination for nonaqueous solvents does not have particular determination, for example can enumerate: the various combinations such as combination of the combination of combination, cyclic carbonates and the lactone of cyclic carbonates and linear carbonate class, three kinds of cyclic carbonates and linear carbonate class.
As electrolyte, for example can enumerate: LiPF
6, LiBF
4, LiClO
4, LiN (SO
2CF
3)
2, LiN (SO
2C
2F
5)
2, LiC (SO
2CF
3)
3, LiPF
4(CF
3)
2, LiPF
3(C
2F
5)
3, LiPF
3(CF
3)
3, LiPF
3(different C
3F
7)
3, LiPF
5(different C
3F
7) etc.These electrolyte can use wherein a kind of, also it can be used in combination.These electrolyte dissolutions back in above-mentioned nonaqueous solvents can be used, its working concentration is generally 0.1～3M, is preferably 0.5～1.5M.
Electrolyte of the present invention can be by nonaqueous solvents mixing that for example will be above-mentioned, to wherein being dissolved into above-mentioned electrolyte and being dissolved at least a making in the above-mentioned organic compound.
Electrolyte of the present invention preferably uses as the constituent material of secondary cell, and especially preferably the constituent material as lithium secondary battery uses.Do not have particular determination for the constituent material beyond the electrolyte that constitutes secondary cell, can use the various constituent materials that in the past used.
For example, as positive active material, can use the composite metal oxide that forms with lithium that contains cobalt or nickel.As this class composite metal oxide, for example can enumerate LiCoO
2, LiNiO
2, LiCo
1-xNi
xO
2(0.01＜x＜1) etc.In addition, also can be with LiCoO
2And LiMn
2O
4, LiCoO
2And LiNiO
2, LiMn
2O
4And LiN
iO
2Suitably mixing the back uses.
Positive pole can be according to following step manufacturing, that is: with above-mentioned positive active material and acetylene black, the conductive agent of carbon black etc. and polytetrafluoroethylene (PTFE), Kynoar (PVDF), the copolymer of styrene and butadiene (SBR), the copolymer of acrylonitrile and butadiene (NBR), the binding agent of carboxymethyl cellulose (CMC) etc. is mixing together to make anode mixture, then this positive electrode is rolled on as the metal forming of the aluminium of collector body or stainless steel or lath, then under the temperature about 50 ℃～250 ℃ and carrying out heat treated under the vacuum about 2 hours, thereby make positive pole.
As negative pole (negative electrode active material), can use lithium metal, lithium alloy or can occlusion and emit the material of the carbonaceous material [thermal decomposition charcoal class, coke class, graphite-like (Delanium, native graphite etc.), organic high molecular compound burner body, carbon fiber] of lithium or compound tin-oxide etc.Especially preferably using those intervals of faces with lattice plane (002) (d002) is the carbonaceous material of the graphite mould crystalline texture of 0.335～0.340nm.Should illustrate, can be mixing with the binding agent of ethylene-propylene-diene terpolymer (EPDM), polytetrafluoroethylene (PTFE), Kynoar (PVDF), Styrene-Butadiene (SBR), acrylonitrile-butadiene copolymer (NBR), carboxymethyl cellulose (CMC) etc. the such dusty material of carbonaceous material, use as cathode agent.
Structure to lithium secondary battery does not have particular determination, for example can enumerate the coin type battery or the polymer battery of positive pole, negative pole and barrier film with single or multiple lift and have the cylinder battery of positive pole cylindraceous, negative pole and cylindric barrier film or square battery etc.Should illustrate,, can use known polyolefinic micro-porous film, woven cloths, nonwoven fabrics etc. as barrier film.
Even lithium secondary battery of the present invention shows good cycle characteristics in maximum working voltage also can be between long-term under greater than the situation of 4.2V, the occasion of particularly working as maximum working voltage and be 4.3V also has good cycle characteristics.Cut-ff voltage can be more than 2.0V, also can be more than 2.5V.Current value is not had particular determination, but can use by the constant current discharge of 0.1～3C usually.In addition, lithium secondary battery of the present invention can use in-40～100 ℃ wide temperature range, but preferably uses in 0～80 ℃ temperature range.
Enumerate embodiment below and comparative example specifically describes the present invention.
Embodiment 1
(mensuration of oxidizing potential)
LiPF6 is dissolved in the nonaqueous solvents of propylene carbonate by the concentration of 1M, has made electrolyte,, make 2-methyl-2-phenylpropane become 2 weight % with respect to the concentration of electrolyte then to wherein adding 2-methyl-2-phenylpropane.Use the electrochemical analyser (608A type) of ALS corporate system to measure oxidizing potential down then in room temperature (20 ℃).Use metallic lithium foil as reference electrode, use platinum bar electrode (diameter 1mm) as work electrode.Be scanned up to+6V from+3V according to the speed of per second 10mV.Potential value when the electric current that can observe 0.1mA is changed is as oxidizing potential.But to behind the decimal point the 2nd round up.The oxidizing potential that the result records 2-methyl-2-phenylpropane is 4.9V.
(preparation of electrolyte)
The nonaqueous solvents of preparation EC/PC/DEC (volume ratio)=30/5/65 is to the LiPF that wherein is dissolved into 1M concentration
6With preparation electrolyte, be the 2-methyl-2-phenylpropane of 2 weight % to wherein adding then with respect to electrolyte.
(manufacturing of lithium secondary battery and the mensuration of battery behavior)
With LiCoO
2(positive active material) 90 weight %, acetylene black (conductive agent) 5 weight % and Kynoar (binding agent) 5 weight % mix, to wherein adding 1-Methyl-2-Pyrrolidone and with its furnishing pasty state, then this pastel being coated on the aluminium foil.And then be dried and extrusion forming, thereby make positive pole.In addition, Delanium (negative electrode active material) 95 weight %/Kynoar (binding agent) 5 weight % are mixed, to wherein adding 1-Methyl-2-Pyrrolidone and, then this pastel being coated on the Copper Foil its furnishing pasty state.And then be dried and extrusion forming, thereby make negative pole.Use the little porous film of polypropylene as barrier film then, inject above-mentioned electrolyte, made the cylinder battery that is of a size of 18650 (diameter 18mm, height is 65mm).In battery, be provided with pressure opening port and internal current shearing device.
In order to use this 18650 battery to carry out cyclic test, the constant current charge of pressing 1.45A (1C) down at high temperature (45 ℃) is to 4.2V, is that to continue to charge to total charging time under constant voltage be 3 hours to final voltage then with 4.2V.Under the constant current of 1.45A (1C), be discharged to final voltage 2.5V then, carry out this repeatedly and discharge and recharge operation.Compare as the occasion (comparative example 1) of electrolyte with using 1M LiPF6+EC/PC/DEC (volume ratio)=30/5/65, the initial stage discharge capacity of the two equates.Measure its battery behavior after 300 circulations, the result shows that when being 100% with the initial stage discharge capacity, the discharge capacity sustainment rate after 300 circulations is 85.5%.In addition, the high temperature preservation characteristics is also good.And then, use this through having carried out 18650 batteries of 300 cyclic tests repeatedly, under normal temperature (20 ℃), press the constant current continuation charging of 2.9A (2C) from fully charged state, so carry out overcharge test.At this moment, the failure of current time is 25 minutes, and the battery maximum surface temperature behind the failure of current is 68 ℃.The material condition and the battery behavior that are of a size of 18650 cylinder battery are shown in Table 1.
Embodiment 2
Except using with respect to electrolyte is the 2-methyl-2-phenylpropane of 5 weight %, and all the other measure oxidizing potential similarly to Example 1.The results are shown in the table 1.In addition, be of a size of that the maximum surface temperature of battery is shown in Table 1 after the material condition, discharge capacity sustainment rate, failure of current time and failure of current after 300 circulations of 18650 cylinder battery.
Embodiment 3
Respectively do for oneself the 2-methyl-2-phenylpropane and cyclohexyl benzene of 1 weight % except using with respect to electrolyte, all the other measure oxidizing potential similarly to Example 1.The results are shown in the table 1.In addition, be of a size of that the maximum surface temperature of battery is shown in Table 1 after the material condition, discharge capacity sustainment rate, failure of current time and failure of current after 300 circulations of 18650 cylinder battery.Compare with embodiment 1, the temperature of present embodiment behind failure of current is lower, and the failure of current time is also shorter, this shows, the effect that overcharges that prevents of present embodiment is better than embodiment 1.
Embodiment 4
Except using with respect to electrolyte is that all the other measure oxidizing potential similarly to Example 1 the 1-bromo-4-2-methyl-2-phenylpropane of 2 weight %.The results are shown in the table 1.In addition, be of a size of that the maximum surface temperature of battery is shown in Table 1 after the material condition, discharge capacity sustainment rate, failure of current time and failure of current after 300 circulations of 18650 cylinder battery.
Comparative example 1
Except not adding 1-bromo-4-2-methyl-2-phenylpropane, all the other measure oxidizing potential similarly to Example 1.The results are shown in the table 1.In addition, be of a size of that the maximum surface temperature of battery is shown in Table 1 after the material condition, discharge capacity sustainment rate, failure of current time and failure of current after 300 circulations of 18650 cylinder battery.
Comparative example 2～4
Replace the 1-bromo-4-2-methyl-2-phenylpropane except adding with respect to respectively do for oneself 4-fluoroanisole (comparative example 2), 2-chlorothiophene (comparative example 3) or the biphenyl (comparative example 4) of 2 weight % of electrolyte, all the other measure oxidizing potential similarly to Example 1.The results are shown in the table 1.In addition, be of a size of that the maximum surface temperature of battery is shown in Table 1 after the material condition, discharge capacity sustainment rate, failure of current time and failure of current after 300 circulations of 18650 cylinder battery.
Embodiment 5
Except using LiNi
0.8Co
0.2O
2Replace LiCoO
2As positive active material, in addition, the nonaqueous solvents of preparation EC/PC/VC/DEC (volume ratio)=30/5/2/63 is to wherein being dissolved into LiPF
6With the electrolyte of preparation 1M concentration, be outside the 2-methyl-2-phenylpropane of 3 weight % to wherein adding then with respect to electrolyte, all the other similarly to Example 1 manufacturing dimension be 18650 cylinder battery and measure battery performance.The material condition and the battery behavior that are of a size of 18650 cylinder battery are shown in Table 1.
Embodiment 6
Except using LiNi
0.8Co
0.2O
2Replace LiCoO
2As positive active material, in addition, the nonaqueous solvents of preparation EC/PC/VC/DEC (volume ratio)=30/5/2/63 is to wherein being dissolved into LiPF
6Electrolyte with preparation 1M concentration, be the tert-butyl benzene of 2 weight % and be outside the cyclohexyl benzene of 1 weight % to wherein adding then with respect to electrolyte with respect to electrolyte, all the other similarly to Example 1 manufacturing dimension be 18650 cylinder battery and measure battery performance.The material condition and the battery behavior that are of a size of 18650 cylinder battery are shown in Table 1.
Comparative example 5
Except using LiNi
0.8Co
0.2O
2Replace LiCoO
2Outside positive active material, all the other and comparative example 1 similarly manufacturing dimension are 18650 cylinder battery and measure battery performance.The material condition and the battery behavior that are of a size of 18650 cylinder battery are shown in Table 1.
Embodiment 7
Except using with respect to electrolyte is that the tert-amyl benzene of 2 weight % replaces the 2-methyl-2-phenylpropane, all the other similarly to Example 1 manufacturing dimension be 18650 cylinder battery and measure battery performance.The material condition and the battery behavior that are of a size of 18650 cylinder battery are shown in Table 2.
Embodiment 8
Respectively do for oneself the 2-methyl-2-phenylpropane of 2 weight % and tert-amyl benzene as the organic compound except using with respect to electrolyte, all the other similarly to Example 1 manufacturing dimension be 18650 cylinder battery and measure battery performance.The material condition and the battery behavior that are of a size of 18650 cylinder battery are shown in Table 2.
Embodiment 9
Be respectively the tert-amyl benzene of 2 weight % and 1 weight % and cyclohexyl benzene as the organic compound except using with respect to electrolyte, all the other similarly to Example 1 manufacturing dimension be 18650 cylinder battery and measure battery performance.The material condition and the battery behavior that are of a size of 18650 cylinder battery are shown in Table 2.
Embodiment 10
Except using the 2-methyl-2-phenylpropane, tert-amyl benzene and the cyclohexyl benzene that are respectively 2 weight %, 2 weight % and 1 weight % with respect to electrolyte as the organic compound, all the other similarly to Example 1 manufacturing dimension be 18650 cylinder battery and measure battery performance.The material condition and the battery behavior that are of a size of 18650 cylinder battery are shown in Table 2.
In above embodiment, each embodiment has the cobalt of q.s or nickel to separate out on negative pole when overcharging.As can be seen, the battery that has added organic compound of the present invention battery that the safety-type that overcharges and cycle characteristics all are better than comparative example.
Table 1
| Anodal | Negative pole | Organic compound: amount (wt%) | Oxidizing potential (V) | Electrolyte is formed (volume ratio) | The failure of current time (branch) | The maximum temperature of battery (℃) | Discharge capacity sustainment rate % after 300 circulations | |
| Embodiment 1 | ??LiCoO 2 | Delanium | 2-methyl-2-phenylpropane: 2 | ??4.9 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ??25 | ??68 | ??85.5 |
| Embodiment 2 | ??LiCoO 2 | Delanium | 2-methyl-2-phenylpropane: 5 | ??4.9 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ??23 | ??66 | ??85.1 |
| Embodiment 3 | ??LiCoO 2 | Delanium | 2-methyl-2-phenylpropane: 1+ cyclohexyl benzene: 1 | ??4.9 ??+ ??4.7 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ??18 | ??64 | ??85.3 |
| Embodiment 4 | ??LiCoO 2 | Delanium | 1-bromo-4-2-methyl-2-phenylpropane: 2 | ??4.9 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ??26 | ??69 | ??85.2 |
| Comparative example 1 | ??LiCoO 2 | Delanium | Do not have | ??5.4 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ??31 | Thermal runaway | ??82.8 |
| Comparative example 2 | ??LiCoO 2 | Delanium | 4-fluoroanisole: 2 | ??4.5 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ??22 | ??118 | ??72.6 |
| Comparative example 3 | ??LiCoO 2 | Delanium | 2-chlorothiophene: 2 | ??4.4 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ??19 | ??92 | ??73.3 |
| Comparative example 4 | ??LiCoO 2 | Delanium | Biphenyl: 2 | ??4.5 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ??18 | ??83 | ??74.2 |
| Embodiment 5 | ??LiNi 0.8??Co 0.2O 2 | Delanium | 2-methyl-2-phenylpropane: 3 | ??4.9 | ????1M?LiPF 6????EC/PC/VC/DEC ????＝30/5/2/63 | ??24 | ??67 | ??84.7 |
| Embodiment 6 | ??LiNi 0.8??Co 0.2O 2 | Delanium | 2-methyl-2-phenylpropane: 2+ cyclohexyl benzene: 1 | ??4.9 ??+ ??4.7 | ????1M?LiPF 6????EC/PC/VC/DEC ????＝30/5/2/63 | ??19 | ??65 | ??84.3 |
| Comparative example 5 | ??LiNi 0.8??Co 0.2O 2 | Delanium | Do not have | ??5.4 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ??31 | Thermal runaway | ??80.4 |
Table 2
| Anodal | Negative pole | Organic compound: amount (wt%) | Oxidizing potential (V) | Electrolyte is formed (volume ratio) | The failure of current time (branch) | The maximum temperature of battery (℃) | Discharge capacity sustainment rate % after 300 circulations | |
| Embodiment 7 | ????LiCoO 2 | Delanium | Tert-amyl benzene: 2 | ??4.8 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ????22 | ????66 | ???85.3 |
| Embodiment 8 | ????LiCoO 2 | Delanium | 2-methyl-2-phenylpropane: 2+ tert-amyl benzene: 2 | ??4.9 ??+ ??4.8 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ????20 | ????64 | ???85.2 |
| Embodiment 9 | ????LiCoO 2 | Delanium | Tert-amyl benzene: 2+ cyclohexyl benzene: 1 | ??4.8 ??+ ??4.7 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ????17 | ????63 | ???84.7 |
| Embodiment 10 | ????LiCoO 2 | Delanium | 2-methyl-2-phenylpropane: 2+ tert-amyl benzene: 2+ cyclohexyl benzene: 1 | ??4.9 ??+ ??4.8 ??+ ??4.7 | ????1M?LiPF 6????EC/PC/DEC ????＝30/5/65 | ????17 | ????63 | ???84.9 |
Should illustrate that the present invention is not limited to the embodiment of record, all be possible according to the design of the present invention various combinations released of class easily.Particularly unqualified to the combination of the solvent of the foregoing description.In addition, be of a size of 18650 cylinder battery though the foregoing description only relates to, the present invention also is applicable to the battery of square, aluminium lamination die mould, coin type.
Industrial applicibility
Lithium secondary battery of the present invention is all good at the battery behavior of the security that prevents that battery from overcharging etc. and cycle characteristics, capacitance, preservation characteristics etc.
Claims (19)
1. method that is used to suppress the rapid heating that lithium secondary battery causes when overcharging, this lithium secondary battery is made of anodal, negative pole and nonaqueous electrolytic solution; Wherein, positive pole is made of the composite metal oxide of lithium and cobalt or the composite metal oxide of lithium and nickel; Negative pole by lithium metal, lithium alloy or can occlusion, the material of emitting lithium constitutes; Nonaqueous electrolytic solution by electrolyte dissolution in nonaqueous solvents and constitute, it is characterized in that, be dissolved with organic compound in this nonaqueous electrolytic solution in advance, this organic compound decomposes when overcharging, owing to the effect of this decomposition product makes cobalt or the nickel stripping in the positive pole and separates out on negative pole.
2. the method for claim 1, wherein prevent that by the cobalt or the nickel of on negative pole, separating out lithium and the contact between the electrolyte in the negative pole from suppressing heating.
3. the short circuit that the method for claim 1, wherein causes inside battery by the cobalt of separating out or nickel on negative pole suppresses heating.
4. lithium secondary battery, this lithium secondary battery is made of anodal, negative pole and nonaqueous electrolytic solution; Wherein, positive pole is made of the composite metal oxide of lithium and cobalt or the composite metal oxide of lithium and nickel; Negative pole by lithium metal, lithium alloy or can occlusion, the material of emitting lithium constitutes; Nonaqueous electrolytic solution by electrolyte dissolution in nonaqueous solvents and constitute, it is characterized in that, this nonaqueous electrolytic solution contains organic compound, this organic compound can decompose when lithium secondary battery overcharges, owing to the effect of this decomposition product makes cobalt or the nickel stripping in the positive pole and separates out on negative pole.
5. lithium secondary battery as claimed in claim 4, wherein, above-mentioned organic compound for have with respect to lithium+4.6V～+ organic compound of the oxidizing potential of 5.0V scope.
6. lithium secondary battery as claimed in claim 5, wherein, above-mentioned organic compound is the tertiary alkyl benzene derivative.
7. lithium secondary battery as claimed in claim 6, wherein, above-mentioned tertiary alkyl benzene derivative is 2-methyl-2-phenylpropane, 1-bromo-4-2-methyl-2-phenylpropane or tert-amyl benzene.
8. lithium secondary battery as claimed in claim 4, wherein, above-mentioned organic compound is made up by tertiary alkyl benzene derivative and cyclohexyl benzene and constitutes.
9. lithium secondary battery as claimed in claim 4, wherein, the content of above-mentioned organic compound is with respect to the scope of electrolyte at 0.1～10 weight %.
10. lithium secondary battery, this lithium secondary battery is made of anodal, negative pole and nonaqueous electrolytic solution; Wherein, positive pole is made of the composite metal oxide of lithium and cobalt or the composite metal oxide of lithium and nickel; Negative pole by lithium metal, lithium alloy or can occlusion, the material of emitting lithium constitutes; Nonaqueous electrolytic solution, is characterized in that in nonaqueous solvents and constitute by electrolyte dissolution, this nonaqueous electrolytic solution contain with respect to lithium have+4.6V～+ organic compound of the oxidizing potential of 5.0V scope.
11. lithium secondary battery as claimed in claim 10, wherein, above-mentioned organic compound is the tertiary alkyl benzene derivative.
12. lithium secondary battery as claimed in claim 11, wherein, above-mentioned tertiary alkyl benzene derivative is 2-methyl-2-phenylpropane, 1-bromo-4-2-methyl-2-phenylpropane or tert-amyl benzene.
13. lithium secondary battery as claimed in claim 10, wherein, above-mentioned organic compound is made up by tertiary alkyl benzene derivative and cyclohexyl benzene and constitutes.
14. lithium secondary battery as claimed in claim 10, wherein, the content of above-mentioned organic compound is with respect to the scope of electrolyte at 0.1～10 weight %.
15. a lithium nonaqueous electrolytic solution, this nonaqueous electrolytic solution can be used for the lithium secondary battery that is made of anodal, negative pole and nonaqueous electrolytic solution, wherein, anodally are made of the composite metal oxide of lithium and cobalt or the composite metal oxide of lithium and nickel; Negative pole by lithium metal, lithium alloy or can occlusion, the material of emitting lithium constitutes; Nonaqueous electrolytic solution is made of in nonaqueous solvents electrolyte dissolution; It is characterized in that, this nonaqueous electrolytic solution contain with respect to lithium have+4.6V～+ organic compound of the oxidizing potential of 5.0V scope.
16. nonaqueous electrolytic solution as claimed in claim 15, wherein, above-mentioned organic compound is the tertiary alkyl benzene derivative.
17. nonaqueous electrolytic solution as claimed in claim 16, wherein, above-mentioned tertiary alkyl benzene derivative is 2-methyl-2-phenylpropane, 1-bromo-4-2-methyl-2-phenylpropane or tert-amyl benzene.
18. nonaqueous electrolytic solution as claimed in claim 15, wherein, above-mentioned organic compound is the composition of tertiary alkyl benzene derivative and cyclohexyl benzene.
19. nonaqueous electrolytic solution as claimed in claim 15, wherein, the content of above-mentioned organic compound is with respect to the scope of electrolyte at 0.1～10 weight %.
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| CN102142577A (en) * | 2010-01-28 | 2011-08-03 | 索尼公司 | Nonaqueous electrolyte battery |
| CN110120500A (en) * | 2018-02-05 | 2019-08-13 | 丰田自动车株式会社 | The manufacturing method of metal secondary batteries cathode, metal secondary batteries and metal secondary batteries |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3669024B2 (en) * | 1995-05-26 | 2005-07-06 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
| CA2156800C (en) * | 1995-08-23 | 2003-04-29 | Huanyu Mao | Polymerizable aromatic additives for overcharge protection in non-aqueous rechargeable lithium batteries |
| JP3275998B2 (en) * | 1997-03-28 | 2002-04-22 | 日立マクセル株式会社 | Organic electrolyte secondary battery |
-
2001
- 2001-10-03 CN CNB018200052A patent/CN100344027C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142577A (en) * | 2010-01-28 | 2011-08-03 | 索尼公司 | Nonaqueous electrolyte battery |
| CN110120500A (en) * | 2018-02-05 | 2019-08-13 | 丰田自动车株式会社 | The manufacturing method of metal secondary batteries cathode, metal secondary batteries and metal secondary batteries |
| CN110120500B (en) * | 2018-02-05 | 2022-04-15 | 丰田自动车株式会社 | Negative electrode for metal secondary battery, and method for manufacturing metal secondary battery |
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|---|---|
| CN100344027C (en) | 2007-10-17 |
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