CN118281331A - Nonaqueous electrolyte and secondary battery - Google Patents
Nonaqueous electrolyte and secondary battery Download PDFInfo
- Publication number
- CN118281331A CN118281331A CN202310775987.3A CN202310775987A CN118281331A CN 118281331 A CN118281331 A CN 118281331A CN 202310775987 A CN202310775987 A CN 202310775987A CN 118281331 A CN118281331 A CN 118281331A
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- CN
- China
- Prior art keywords
- additive
- ether
- propionitrile
- battery
- group
- 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.)
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 38
- 239000000654 additive Substances 0.000 claims abstract description 96
- 230000000996 additive effect Effects 0.000 claims abstract description 89
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 229920005554 polynitrile Polymers 0.000 claims abstract description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 102
- -1 pimelic dinitrile Chemical compound 0.000 claims description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 36
- 229910001416 lithium ion Inorganic materials 0.000 claims description 36
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 30
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 7
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 6
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- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 6
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 3
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- 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
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 description 1
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- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
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- 238000004513 sizing Methods 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- Secondary Cells (AREA)
Abstract
In order to overcome the problem that the existing nitrile additive deteriorates the low-temperature performance of a battery, the invention provides a nonaqueous electrolyte, which comprises a solvent, electrolyte salt and an additive, wherein the additive comprises an additive A and an additive B, and the additive A is obtained by bonding a compound shown in a structural formula I with at least one of a group A or a group B; wherein in the structural formula I, an oxygen atom of a hydroxyl group is bonded with one or two of a group A and a group B, and the bonding position is represented; The additive B is selected from polynitrile compounds shown in a structural formula II and/or a structural formula III:
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a nonaqueous electrolyte and a secondary battery.
Background
The appearance of lithium ion batteries accelerates the development of the modern electronic information industry to portability and light weight. The lithium ion battery has the excellent performances of high open circuit voltage, high energy density, small self-discharge rate, long service life, no memory effect, no pollution and the like, and is widely applied to portable consumer electronic devices such as mobile phones, notebook computers, digital cameras, MP3 and the like, but the application of the lithium ion battery to large-scale devices such as electric automobiles, energy storage devices and the like is still in a development stage.
In lithium ion batteries, the quality of the electrolyte has a relatively important impact on its performance. The main development strategy of the electrolyte is to form stable protective films on the positive electrode and the negative electrode of the battery by utilizing the functional additive, so that the chemical reaction between the electrode material and the electrolyte is slowed down, and meanwhile, the permeability of lithium ions is improved, thereby reducing the internal resistance of the lithium ion battery and prolonging the service life of the battery. The nitrile additive which is commonly used at present can form an interfacial film on the surfaces of the anode and the cathode of the battery, so that the electrolyte is reduced to be decomposed and produce gas by reacting with the electrode interface under the high-temperature condition. However, the interfacial film formed by the nitrile additive has the problem of uneven film surface thickness, which can improve high-temperature cycle performance and also cause high battery impedance to affect low-temperature performance of the battery.
Disclosure of Invention
Aiming at the problem that the existing nitrile additive deteriorates the low-temperature performance of the battery, the invention provides a non-aqueous electrolyte and a secondary battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
In one aspect, the invention provides a nonaqueous electrolyte, which comprises a solvent, electrolyte salt and an additive, wherein the additive comprises an additive A and an additive B, and the additive A is obtained by bonding a compound shown in a structural formula I with at least one of a group A or a group B;
Wherein n is 0 or 1; r 1、R2、R3、R4、R5 is independently selected from an alkoxy group of H, C 1～C5, a hydroxyl group or an alkyl group containing a hydroxyl group and having a carbon number of C 1～C5, and R 1～R5 contains at least 4 hydroxyl groups;
wherein in the structural formula I, an oxygen atom of a hydroxyl group is bonded with one or two of a group A and a group B, and the bonding position is represented;
The additive B is selected from polynitrile compounds shown in a structural formula II and/or a structural formula III:
Wherein R 21、R31、R32 and R 33 are each independently selected from substituted or unsubstituted C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C6-C8 aryl or C3-C12 alkoxy; r 22 is selected from H or cyano.
Optionally, the additive a is selected from one or more of the following compounds:
Optionally, the polynitrile compound shown in the structural formula II is selected from one or more of the following compounds:
1,3, 5-pentanetronitrile, 1,3, 6-hexanetricarbonitrile, succinonitrile, glutaronitrile, adipodinitrile, pimelic dinitrile, suberonitrile, nonyldinitrile, decyldinitrile.
Optionally, the polynitrile compound shown in the structural formula III is selected from one or more of the following compounds:
Ethylene glycol bis (propionitrile) ether, 1, 2-propylene glycol bis (propionitrile) ether, glycerol tris (propionitrile) ether (CAS No. 2465-93-2), erythritol tetrakis (propionitrile) ether (CAS No. 782474-63-9), xylitol penta (propionitrile) ether (CASNo.55726-81-3), mannitol hexa (propionitrile) ether (CAS No. 21412-40-8), sorbitol hexa (propionitrile) ether (CAS No. 77209-70-2), galactitol hexa (propionitrile) ether (CAS No. 146338-87-6).
Optionally, the additive B is selected from one or more of the following compounds:
Succinonitrile, glutaronitrile, 1,3, 6-hexanedinitrile, adiponitrile, pimelic dinitrile, suberonitrile, nonodinitrile, sebaconitrile, ethylene glycol bis (propionitrile) ether, 1, 2-propanediol bis (propionitrile) ether, glycerol tris (propionitrile) ether, erythritol tetrakis (propionitrile) ether, xylitol penta (propionitrile) ether, mannitol hexa (propionitrile) ether, sorbitol hexa (propionitrile) ether, galactitol hexa (propionitrile) ether.
Optionally, the mass percentage of the additive A is 0.05-10% and the mass percentage of the additive B is 0.05-5% based on 100% of the total mass of the nonaqueous electrolyte.
Optionally, the electrolyte salt comprises a lithium salt selected from at least one of LiPF6、LiBOB、LiDFOB、LiPO2F2、LiBF4、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO2F)2、LiClO4、LiAlCl4、LiCF3SO3、Li2B10Cl10、 lower aliphatic carboxylic acid lithium salts;
the concentration of the lithium salt is 0.1mol/L to 8mol/L.
Optionally, the organic solvent includes at least one of an ether solvent, a nitrile solvent, a carbonate solvent, a carboxylate solvent, and a sulfone solvent.
In another aspect, the present invention provides a secondary battery comprising a positive electrode, a negative electrode, and a nonaqueous electrolyte as described above.
Optionally, the secondary battery is a lithium metal battery, a lithium ion battery or a lithium sulfur battery.
According to the nonaqueous electrolytic solution provided by the invention, a combination of an additive A and an additive B is adopted as a film-forming additive. The additive A has a sulfate structure, electrons can be obtained on the surface of the anode material to form a conductive interface containing lithium sulfate, and sulfate units in the structure can respectively form free radicals and further react with other sulfate units to form a stable, crosslinked and ductile SEI film; additive a also contains ether linkages, possibly functioning like PEO lithium-conducting, thereby reducing cell impedance. The cyano group and cyanoethoxy group of the additive B can react with HF to inhibit acid generation and inhibit gas generation. Improving the voltage tolerance of the electrolyte. When the additive A and the additive B are used together, the additive A and the additive B participate in the formation of the passivation film on the surface of the electrode together, and the obtained passivation film has good ion conduction efficiency and high-temperature stability. The impedance is reduced while inhibiting the gas generation of the nonaqueous electrolyte and the electrode interface reaction under the high temperature condition, and the high temperature performance and the low temperature performance of the battery can be effectively considered.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a nonaqueous electrolyte, which comprises a solvent, electrolyte salt and an additive, wherein the additive comprises an additive A and an additive B, and the additive A is obtained by bonding a compound shown in a structural formula I with at least one of a group A or a group B;
Wherein n is 0 or 1; r 1、R2、R3、R4、R5 is independently selected from an alkoxy group of H, C 1～C5, a hydroxyl group or an alkyl group containing a hydroxyl group and having a carbon number of C 1～C5, and R 1～R5 contains at least 4 hydroxyl groups;
Wherein in the structural formula I, an oxygen atom containing a hydroxyl is bonded with one or two of a group A and a group B, and the bonding position is represented;
Specifically, in the structural formula I, R 1、R2、R3、R4、R5 can be the same or different, the application is not limited, and it is noted that R 1、R2、R3、R4、R5 must contain at least 4 hydroxyl functional groups. In the structural formula I, the oxygen atom containing the hydroxyl is bonded with one or two groups A and B, namely the structural formula I can be bonded with two identical groups A or two identical groups B, or can be bonded with one group A and one group B to form a functional additive of sulfate or sulfite with a five-membered ring structure or a functional additive of sulfate or sulfite with a six-membered ring structure.
The additive B is selected from polynitrile compounds shown in a structural formula II and/or a structural formula III:
Wherein R 21、R31、R32 and R 33 are each independently selected from substituted or unsubstituted C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C6-C8 aryl or C3-C12 alkoxy; r 22 is selected from H or cyano.
In the nonaqueous electrolytic solution, a combination of an additive A and an additive B is used as a film-forming additive. The additive A has a sulfate structure, electrons can be obtained on the surface of the anode material to form a lithium-conducting interface containing lithium sulfate, and sulfate units in the structure can respectively form free radicals and further react with other sulfate units to form a stable, crosslinked and ductile SEI film; additive a also contains ether linkages, possibly functioning like PEO lithium-conducting, thereby reducing cell impedance. The cyano group and cyanoethoxy group of the additive B can react with HF to inhibit acid generation, and also has the effects of inhibiting gas generation and improving the voltage tolerance of the electrolyte. When the additive A and the additive B are used together, the additive A and the additive B participate in the formation of the passivation film on the surface of the electrode together, and the obtained passivation film has good ion conduction efficiency and high-temperature stability. The impedance is reduced while inhibiting the gas generation of the nonaqueous electrolyte and the electrode interface reaction under the high temperature condition, and the high temperature performance and the low temperature performance of the battery can be effectively considered.
In some embodiments, the additive a is selected from one or more of the following compounds:
the above is only a preferred compound of the present invention, and does not represent a limitation of the present invention.
The person skilled in the art, knowing the structural formula of the functional additive, can know the method of preparation of the functional additive according to common general knowledge in the field of chemical synthesis. For example: compound 1 arabinogany disulfite can be prepared by the following method: arabinose, ethyl acetate and pyridine are placed in a reaction vessel, and thionyl chloride is added dropwise under the condition of low temperature. After reacting for several hours, filtering, washing the filtrate with saturated saline solution, separating liquid, drying the organic phase with anhydrous magnesium sulfate, carrying out suction filtration, and concentrating under reduced pressure to obtain the compound 1 arabinose disulfite.
Compound 2 arabinose disulfate can be prepared by the following method: the compound 2 arabinose disulfate is obtained by oxidizing sulfite by using oxidant such as sodium hypochlorite after the compound 1 arabinose disulfate is prepared by a preparation method of the compound 1 arabinose disulfate.
In some embodiments, the polynitrile compound of formula ii is selected from one or more of the following compounds:
1,3, 5-pentanetronitrile, 1,3, 6-hexanetricarbonitrile, succinonitrile, glutaronitrile, adipodinitrile, pimelic dinitrile, suberonitrile, nonyldinitrile, decyldinitrile.
In some embodiments, the polynitrile compound of formula iii is selected from one or more of the following compounds:
Ethylene glycol bis (propionitrile) ether, 1, 2-propylene glycol bis (propionitrile) ether, glycerol tris (propionitrile) ether (CAS No. 2465-93-2), erythritol tetrakis (propionitrile) ether (CAS No. 782474-63-9), xylitol penta (propionitrile) ether (CASNo.55726-81-3), mannitol hexa (propionitrile) ether (CAS No. 21412-40-8), sorbitol hexa (propionitrile) ether (CAS No. 77209-70-2), galactitol hexa (propionitrile) ether (CAS No. 146338-87-6).
In some embodiments, the additive B is selected from one or more of the following compounds:
Succinonitrile, glutaronitrile, 1,3, 6-hexanedinitrile, adiponitrile, pimelic dinitrile, suberonitrile, nonodinitrile, sebaconitrile, ethylene glycol bis (propionitrile) ether, 1, 2-propanediol bis (propionitrile) ether, glycerol tris (propionitrile) ether, erythritol tetrakis (propionitrile) ether, xylitol penta (propionitrile) ether, mannitol hexa (propionitrile) ether, sorbitol hexa (propionitrile) ether, galactitol hexa (propionitrile) ether. .
In some embodiments, the mass percentage of the additive A is 0.05% -10% and the mass percentage of the additive B is 0.05% -5% based on 100% of the total mass of the nonaqueous electrolyte.
In a specific embodiment, the mass percentage of the additive a may be 0.05％、0.08％、0.1％、0.5％、0.8％、1％、1.2％、1.5％、1.8％、2％、2.2％、2.5％、2.8％、3％、3.2％、3.5％、3.8％、4％、4.5％、5％、5.5％、6％、6.5％、7％、7.5％、7.8％、8％、8.5％、9％、9.5％ or 10% based on 100% of the total mass of the nonaqueous electrolyte.
In specific embodiments, the additive B may be 0.05%, 0.08%, 0.1%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.5% or 5% by mass based on 100% by mass of the total nonaqueous electrolyte.
In the nonaqueous electrolyte, the addition amount of the additive a and the addition amount of the additive B are related to the film formation quality, and when the addition amount of either the additive a or the additive B is too low, the film formation thickness of the passivation film is not uniform, and the problem of poor stability is caused, the effect of better considering the high-low temperature performance is difficult to achieve, and when the addition amount of either the additive a or the additive B is too high, the increase of the side reaction in the nonaqueous electrolyte is caused, the film formation thickness of the passivation film is increased, and the battery impedance is increased instead, which is unfavorable for the improvement of the low-temperature performance.
In various embodiments, the corresponding electrolyte salt may be selected according to the type of battery applied, and in particular, when the nonaqueous electrolyte solution is applied to a lithium ion battery, the electrolyte salt is selected from lithium salts.
In some embodiments, the electrolyte salt comprises a lithium salt selected from at least one of the group consisting of LiPF6、LiBOB、LiDFOB、LiPO2F2、LiBF4、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO2F)2、LiClO4、LiAlCl4、LiCF3SO3、Li2B10Cl10、 lower aliphatic carboxylic acid lithium salts;
The electrolyte salt in the nonaqueous electrolyte solution is dissociated to form alkali metal ions which are deintercalated and embedded between the positive electrode and the negative electrode to complete charge and discharge circulation, the concentration of the electrolyte salt directly influences the transmission speed of the alkali metal ions, and the transmission speed of the alkali metal ions influences the potential change of the negative electrode. In the process of quick battery charging, the moving speed of alkali metal ions needs to be improved as much as possible, the formation of lithium dendrites caused by too fast negative electrode potential drop is prevented, potential safety hazards are brought to the battery, and meanwhile, the too fast attenuation of the circulating capacity of the battery can be prevented. When the content of the electrolyte salt is too low, the intercalation and deintercalation efficiency of alkali metal ions between the positive electrode and the negative electrode can be reduced, and the requirement of quick charge of the battery can not be met; when the content of the electrolyte salt is too high, the viscosity of the nonaqueous electrolyte is increased, and thus the improvement of the intercalation and deintercalation efficiency of alkali metal ions is also unfavorable, and the internal resistance of the battery is increased.
When the electrolyte salt includes a lithium salt, the concentration of the lithium salt is 0.1mol/L to 8mol/L. In a preferred embodiment, the concentration of the lithium salt is 0.5mol/L to 2.5mol/L. Specifically, the concentration of the electrolyte salt may be 0.5mol/L、1mol/L、1.5mol/L、2mol/L、2.5mol/L、3mol/L、3.5mol/L、4mol/L、4.5mol/L、5mol/L、5.5mol/L、6mol/L、6.5mol/L、7mol/L、7.5mol/L、8mol/L.
In some embodiments, the non-aqueous organic solvent comprises at least one of an ether solvent, a nitrile solvent, a carbonate solvent, a carboxylate solvent, and a sulfone solvent.
In some embodiments, the ethereal solvent includes a cyclic ether or a chain ether, preferably a chain ether having 3 to 10 carbon atoms and a cyclic ether having 3 to 6 carbon atoms, and the cyclic ether may be specifically, but not limited to, one or more of 1, 3-Dioxolane (DOL), 1, 4-Dioxane (DX), crown ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-CH 3 -THF), 2-trifluoromethyl tetrahydrofuran (2-CF 3 -THF); the chain ether may be, but not limited to, dimethoxymethane, diethoxymethane, ethoxymethoxymethane, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl ether, diethylene glycol dimethyl ether. Since the chain ether has high solvation ability with lithium ions and can improve ion dissociation properties, dimethoxymethane, diethoxymethane and ethoxymethoxymethane, which have low viscosity and can impart high ion conductivity, are particularly preferable. The ether compound may be used alone, or two or more of them may be used in any combination and ratio. The amount of the ether compound to be added is not particularly limited, and is arbitrary within a range that does not significantly impair the effect of the highly compacted lithium ion battery of the present invention, and is usually 1% or more, preferably 2% or more, more preferably 3% or more in terms of the volume ratio of the nonaqueous solvent of 100%, and is usually 30% or less, preferably 25% or less, more preferably 20% or less in terms of the volume ratio. When two or more ether compounds are used in combination, the total amount of the ether compounds may be set to satisfy the above range. When the amount of the ether compound is within the above preferred range, the effect of improving the ionic conductivity due to the increase in the dissociation degree of lithium ions and the decrease in the viscosity of the chain ether can be easily ensured. In addition, when the negative electrode active material is a carbon material, co-intercalation of the chain ether and lithium ions can be suppressed, and thus the input/output characteristics and the charge/discharge rate characteristics can be brought into appropriate ranges.
In some embodiments, the nitrile solvent may be, but is not limited to, one or more of acetonitrile, glutaronitrile, malononitrile.
In some embodiments, the carbonate-based solvent includes a cyclic carbonate or a chain carbonate, which may be specifically but not limited to one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), gamma-butyrolactone (GBL), butylene Carbonate (BC); the chain carbonate may be, but is not limited to, in particular, one or more of dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), dipropyl carbonate (DPC). The content of the cyclic carbonate is not particularly limited, and is arbitrary within a range that does not significantly impair the effect of the lithium ion battery of the present invention, but in the case of using one of them alone, the lower limit of the content is usually 3% by volume or more, preferably 5% by volume or more, relative to the total amount of the solvent of the nonaqueous electrolytic solution. By setting the range, it is possible to avoid a decrease in conductivity due to a decrease in dielectric constant of the nonaqueous electrolyte solution, and it is easy to achieve a good range of high-current discharge characteristics, stability with respect to the negative electrode, and cycle characteristics of the nonaqueous electrolyte battery. The upper limit is usually 90% by volume or less, preferably 85% by volume or less, and more preferably 80% by volume or less. By setting the range, the oxidation/reduction resistance of the nonaqueous electrolytic solution can be improved, thereby contributing to improvement of stability at high-temperature storage. The content of the chain carbonate is not particularly limited, but is usually 15% by volume or more, preferably 20% by volume or more, and more preferably 25% by volume or more, based on the total amount of the solvent of the nonaqueous electrolytic solution. In addition, the volume ratio is usually 90% or less, preferably 85% or less, and more preferably 80% or less. By setting the content of the chain carbonate in the above range, the viscosity of the nonaqueous electrolytic solution can be easily set to an appropriate range, and the decrease in the ionic conductivity can be suppressed, thereby contributing to the improvement in the output characteristics of the nonaqueous electrolyte battery. When two or more kinds of chain carbonates are used in combination, the total amount of the chain carbonates may be set to satisfy the above range.
In some embodiments, it may also be preferable to use a chain carbonate having a fluorine atom (hereinafter simply referred to as "fluorinated chain carbonate"). The number of fluorine atoms in the fluorinated chain carbonate is not particularly limited as long as it is 1 or more, but is usually 6 or less, preferably 4 or less. In the case where the fluorinated chain carbonate has a plurality of fluorine atoms, these fluorine atoms may be bonded to the same carbon or may be bonded to different carbons. Examples of the fluorinated chain carbonate include fluorinated dimethyl carbonate derivatives, fluorinated ethyl methyl carbonate derivatives, and fluorinated diethyl carbonate derivatives.
The carboxylic acid ester solvent includes a cyclic carboxylic acid ester and/or a chain carbonate. Examples of the cyclic carboxylic acid ester include: one or more of gamma-butyrolactone, gamma-valerolactone and delta-valerolactone. Examples of the chain carbonate include, for example: one or more of Methyl Acetate (MA), ethyl Acetate (EA), propyl acetate (EP), butyl acetate, propyl Propionate (PP) and butyl propionate.
In some embodiments, the sulfone-based solvent includes cyclic sulfones and chain sulfones, preferably compounds having generally 3 to 6 carbon atoms, preferably 3 to 5 carbon atoms in the case of cyclic sulfones, and generally 2 to 6 carbon atoms, preferably 2 to 5 carbon atoms in the case of chain sulfones. The amount of the sulfone-based solvent to be added is not particularly limited, and is arbitrary within a range that does not significantly impair the effect of the lithium ion battery of the present invention, and is usually 0.3% or more by volume, preferably 0.5% or more by volume, more preferably 1% or more by volume, and is usually 40% or less by volume, preferably 35% or less by volume, more preferably 30% or less by volume, based on the total amount of the solvent of the nonaqueous electrolyte. When two or more sulfone solvents are used in combination, the total amount of sulfone solvents may be set to satisfy the above range. When the amount of the sulfone-based solvent added is within the above range, an electrolyte solution excellent in high-temperature storage stability tends to be obtained.
In a preferred embodiment, the solvent is a mixture of cyclic carbonates and chain carbonates.
Another embodiment of the present invention provides a secondary battery including a positive electrode, a negative electrode, and a nonaqueous electrolytic solution as described above.
The secondary battery adopts the non-aqueous electrolyte, so that an SEI film which is uniform and stable, has good strength and toughness can be formed at an electrode interface, the high-temperature storage and cycle performance of the secondary battery are obviously improved, the low-temperature performance of the battery can be optimized, and the impedance of the battery is effectively reduced.
In specific embodiments, the secondary battery is a lithium metal battery, a lithium ion battery, or a lithium sulfur battery.
In some embodiments, the positive electrode includes a positive electrode material layer including a positive electrode active material, and the kind and content of the positive electrode active material are not particularly limited, and may be selected according to actual needs, as long as it is a positive electrode active material or a conversion type positive electrode material capable of reversibly intercalating/deintercalating metal ions (lithium ions, etc.).
In a preferred embodiment, the secondary battery is a lithium ion battery, the positive electrode active material of which may be selected from at least one of LiFe 1-x'M'x'PO4、LiMn2-y'My'O4 and LiNi xCoyMnzM1-x-y-zO2, wherein M ' is selected from at least one of Mn, mg, co, ni, cu, zn, al, sn, B, ga, cr, sr, V or Ti, M is selected from at least one of Fe, co, ni, mn, mg, cu, zn, al, sn, B, ga, cr, sr, V or Ti, and 0.ltoreq.x ' < 1, 0.ltoreq.y '. Ltoreq.1, 0.ltoreq.y.ltoreq.1, 0.ltoreq.x.ltoreq.1, 0.ltoreq.z.ltoreq.1, x+y+z.ltoreq.1, and the positive electrode active material may be further selected from at least one of sulfide, selenide, halide. More preferably, the positive electrode active material may be selected from at least one of LiCoO2、LiFePO4、LiFe0.8Mn0.2PO4、LiMn2O4、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.2Mn0.2Al0.1O2、LiNi0.5Co0.2Al0.3O2.
In some embodiments, the positive electrode further comprises a positive electrode current collector, and the positive electrode material layer is disposed on a surface of the positive electrode current collector.
The positive current collector is selected from a metal material that can conduct electrons, preferably, the positive current collector includes at least one of Al, ni, tin, copper, stainless steel, and in a more preferred embodiment, the positive current collector is selected from aluminum foil.
In some embodiments, the positive electrode active material layer further comprises a positive electrode binder and a positive electrode conductive agent, and the positive electrode active material, the positive electrode binder and the positive electrode conductive agent are blended to obtain the positive electrode material layer.
The positive electrode binder includes thermoplastic resins such as polyvinylidene fluoride, a copolymer of vinylidene fluoride, polytetrafluoroethylene, a copolymer of vinylidene fluoride-hexafluoropropylene, a copolymer of tetrafluoroethylene-perfluoroalkyl vinyl ether, a copolymer of ethylene-tetrafluoroethylene, a copolymer of vinylidene fluoride-trifluoroethylene, a copolymer of vinylidene fluoride-trichloroethylene, a copolymer of vinylidene fluoride-fluoroethylene, a copolymer of vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene, thermoplastic polyimide, polyethylene, polypropylene, and the like; an acrylic resin; and at least one of styrene butadiene rubber.
The positive electrode conductive agent comprises at least one of conductive carbon black, conductive carbon spheres, conductive graphite, conductive carbon fibers, carbon nanotubes, graphene or reduced graphene oxide.
In some embodiments, the anode includes an anode material layer including an anode active material, and the kind and content of the anode active material are not particularly limited and may be selected according to actual requirements.
In a preferred embodiment, the secondary battery is a lithium ion battery, and the negative electrode active material of the secondary battery comprises at least one of a carbon-based negative electrode, a silicon-based negative electrode, a tin-based negative electrode and a lithium negative electrode. Wherein the carbon-based negative electrode may include graphite, hard carbon, soft carbon, graphene, mesophase carbon microspheres, and the like; the silicon-based anode may include a silicon material, an oxide of silicon, a silicon-carbon composite material, a silicon alloy material, or the like; the tin-based negative electrode may include tin, tin carbon, tin oxygen, and tin metal compounds; the lithium negative electrode may include metallic lithium or a lithium alloy. The lithium alloy may specifically be at least one of a lithium silicon alloy, a lithium sodium alloy, a lithium potassium alloy, a lithium aluminum alloy, a lithium tin alloy, and a lithium indium alloy.
In some embodiments, the negative electrode further comprises a negative electrode current collector, and the negative electrode material layer is disposed on a surface of the negative electrode current collector. The material of the negative electrode current collector may be the same as that of the positive electrode current collector, and will not be described again.
In some embodiments, the negative electrode material layer further comprises a negative electrode binder and a negative electrode conductive agent, and the negative electrode active material, the negative electrode binder and the negative electrode conductive agent are blended to obtain the negative electrode material layer. The negative electrode binder and the negative electrode conductive agent may be the same as the positive electrode binder and the positive electrode conductive agent, respectively, and will not be described again here.
In some embodiments, a separator is further included in the secondary battery, the separator being positioned between the positive electrode and the negative electrode.
The membrane can be an existing conventional membrane, and can be a ceramic membrane, a polymer membrane, a non-woven fabric, an inorganic-organic composite membrane and the like, including but not limited to a membrane such as single-layer PP (polypropylene), single-layer PE (polyethylene), double-layer PP/PE, double-layer PP/PP, and three-layer PP/PE/PP.
The invention is further illustrated by the following examples.
Additive a used in the following examples is shown in table 1 below:
TABLE 1
Example 1
The embodiment is used for explaining the preparation method of the nonaqueous electrolyte and the lithium ion battery, and comprises the following operation steps:
1) Preparation of nonaqueous electrolyte:
Ethylene Carbonate (EC), diethyl carbonate (DEC) and ethylmethyl carbonate (EMC) were mixed in a mass ratio EC: DEC: emc=1:1:1, and then lithium hexafluorophosphate (LiPF 6) was added to a molar concentration of 1mol/L, and additives were added in an amount of each additive type and content shown in table 2, based on 100% of the total weight of the nonaqueous electrolytic solution.
2) Preparation of a positive plate:
The positive electrode active material lithium nickel cobalt manganese oxide LiNi 0.6Co0.2Mn0.2O2, conductive carbon black Super-P and binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 95:2:3, and then dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrode slurry. The sizing agent is evenly coated on two sides of the aluminum foil, and the positive plate is obtained after drying, calendaring and vacuum drying, and an aluminum outgoing line is welded by an ultrasonic welder, and the thickness of the positive plate is 120-150 mu m.
3) Preparing a negative plate:
The negative electrode active material artificial graphite, conductive carbon black Super-P, binder styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) were mixed in a mass ratio of 95:1:2:2, and then dispersed in deionized water to obtain a negative electrode slurry. Coating the slurry on two sides of a copper foil, drying, calendaring and vacuum drying, and welding a nickel lead-out wire by an ultrasonic welder to obtain a negative plate, wherein the thickness of the negative plate is 120-150 mu m.
4) Preparation of the battery cell:
And placing a three-layer diaphragm with the thickness of 20 mu m between the positive plate and the negative plate, winding a sandwich structure formed by the positive plate, the negative plate and the diaphragm, flattening the winding body, putting into an aluminum foil packaging bag, and baking for 48 hours at the temperature of 75 ℃ in vacuum to obtain the battery cell to be injected with the liquid.
5) And (3) filling and forming the battery cell:
In a glove box with the dew point controlled below-40 ℃, the prepared electrolyte is injected into a battery cell, and the battery cell is subjected to vacuum packaging and is kept for 24 hours.
Then the first charge is conventionally formed by the following steps: and (3) carrying out constant current charging at 0.05C for 180min, carrying out constant current charging at 0.2C to 3.95V, carrying out secondary vacuum sealing, then further carrying out constant current charging at 0.2C to 4.2V, and carrying out constant current discharging at 0.2C to 3.0V after standing for 24hr at normal temperature to obtain the LiNi 0.6Co0.2Mn0.2O2/artificial graphite lithium ion battery.
Examples 2 to 16
Examples 2 to 16 are for explaining the nonaqueous electrolytic solution and the battery thereof disclosed in the present invention, and include most of the operation steps in example 1, which are different in that:
The types and contents of additives in the preparation of the nonaqueous electrolytic solutions were different, as shown in table 2.
Comparative examples 1 to 23
Comparative examples 1 to 23 are for comparative illustration of the nonaqueous electrolytic solution and the battery thereof disclosed in the present invention, including most of the operation steps in example 1, which are different in that:
The types and contents of additives in the preparation of the nonaqueous electrolytic solutions were different, as shown in table 2.
Performance testing
The following performance tests were performed on the lithium ion batteries prepared in examples 1 to 16 and comparative examples 1 to 23: high temperature storage Performance test
And (3) charging the formed lithium ion battery to 4.2V at normal temperature by using a constant current of 1C, then charging the lithium ion battery to a constant current and constant voltage until the current is reduced to 0.05C, discharging the lithium ion battery to 3.0V by using a constant current of 1C, measuring the initial discharge capacity D1, the initial battery volume V1 and the initial impedance F1 of the battery, then charging the lithium ion battery to full power, storing the lithium ion battery in an environment of 60 ℃ for 30 days, discharging the lithium ion battery to 3V by using 1C, and measuring the holding capacity D2, the recovery capacity D3, the impedance F2 after storage and the battery volume V2 after storage of the battery. The calculation formula is as follows:
battery capacity retention (%) =retention capacity D2/initial capacity d1×100%;
Battery capacity recovery rate (%) =recovery capacity D3/initial capacity d1×100%;
volume expansion ratio (%) = (battery volume after storage V2-initial battery volume V1)/initial battery volume v1×100%;
High temperature cycle performance test
And (3) charging the lithium ion battery after formation to 4.2V at 45 ℃ with a constant current of 1C, charging with a constant current and a constant voltage until the current is reduced to 0.05C, discharging with a constant current of 1C to 3.0V, measuring the discharge capacity of the battery at the first week and the initial impedance of the battery at the first week, and circularly charging and discharging for 1000 weeks according to the method. The calculation formula is as follows:
capacity retention (%) = 1000 th week discharge capacity/first week discharge capacity x 100%;
Internal resistance increase rate (%) = (1000 th week impedance-first week initial impedance)/first week initial impedance×100%.
Low temperature discharge performance test
And (3) charging the lithium ion battery after formation to 4.2V at normal temperature under a constant current of 1C, charging under a constant current and constant voltage until the current is reduced to 0.05C, discharging under a constant current of 1C to 3.0V, measuring the initial discharge capacity C1 of the battery, charging until full charge, placing for 16 hours in an environment of minus 20 ℃, discharging under a constant current of 0.5C to 3V, and measuring the holding capacity C2 of the battery. The calculation formula is as follows:
battery capacity retention (%) =retention capacity C2/initial capacity c1×100%;
the test results obtained are filled in table 2.
TABLE 2
As can be seen from the test results of examples 1 to 10 and comparative examples 1 to 6 and 13 to 17, compared with the nonaqueous electrolyte using the additive a alone or using the additive B alone, the nonaqueous electrolyte simultaneously added with the additive a and the additive B is applied to a lithium ion battery, can more effectively improve the high-temperature cycle performance and the high-temperature storage performance of the lithium ion battery, has a better improving effect on the low-temperature discharge performance of the lithium ion battery, and shows that the additive a and the additive B have a better synergistic effect, wherein cyano groups and cyanoethoxy groups in the additive B can react with HF to inhibit the generation of acid, and simultaneously has an effect of inhibiting gas production. The electrolyte voltage tolerance improving effect is achieved, meanwhile, the problem that the impedance of the interface film formed by the participation of the additive B is large is solved, the additive A is added, a sulfate unit in the additive A can form free radicals and further reacts with another sulfate unit to form a stable, crosslinked and tough SEI film, ether bonds in the additive A have a PEO lithium conducting function, so that the internal impedance of a battery is reduced, the obtained passivation film has good ion conduction efficiency and high-temperature stability, the impedance is reduced while the gas production of the non-aqueous electrolyte and electrode interface reaction is inhibited under the high-temperature condition, and the high-temperature performance and the low-temperature performance of the battery can be effectively considered.
From the test results of examples 1 to 6, it is understood that, in the nonaqueous electrolyte provided by the present invention, when the addition amount of the additive B is fixed, as the addition amount of the additive a increases, the high-temperature cycle capacity retention rate, the high-temperature storage capacity retention rate, the low-temperature discharge capacity retention rate, and the like of the obtained lithium ion battery all show a tendency of increasing first and then decreasing second; from the test results of examples 7 to 10, it was revealed that when the amount of additive a added was fixed, the low-temperature discharge capacity retention rate of the resulting lithium ion battery gradually deteriorated with an increase in the amount of additive B added, indicating that the addition of additive B resulted in an increase in interfacial film resistance, deteriorating low-temperature performance, and that this problem could be better solved by the addition of additive a, and that when additive a and additive B were in a proper compounding condition, high-low temperature performance of the battery could be ensured.
As can be seen from the test results of examples 11 to 16 and comparative examples 7 to 12 and 18 to 23, the electrolyte system provided by the invention adopts different types of additives A and different types of additives B for combination, and the obtained lithium ion battery has better high-low temperature electrochemical performance, which indicates that the electrolyte system provided by the invention is applicable to different additives A and additives B and has universality.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The non-aqueous electrolyte is characterized by comprising a solvent, electrolyte salt and an additive, wherein the additive comprises an additive A and an additive B, and the additive A is obtained by bonding a compound shown in a structural formula I with at least one of a group A or a group B;
Wherein n is 0 or 1; r 1、R2、R3、R4、R5 is independently selected from an alkoxy group of H, C 1～C5, a hydroxyl group or an alkyl group containing a hydroxyl group and having a carbon number of C 1～C5, and R 1～R5 contains at least 4 hydroxyl groups;
Wherein in the structural formula I, an oxygen atom containing a hydroxyl is bonded with one or two of a group A and a group B, and the bonding position is represented;
The additive B is selected from polynitrile compounds shown in a structural formula II and/or a structural formula III:
Wherein R 21、R31、R32 and R 33 are each independently selected from substituted or unsubstituted C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C6-C8 aryl or C3-C12 alkoxy; r 22 is selected from H or cyano.
2. The nonaqueous electrolyte according to claim 1, wherein the additive a is selected from one or more of the following compounds:
3. The nonaqueous electrolyte according to claim 1, wherein the polynitrile compound represented by the structural formula ii is selected from one or more of the following compounds:
1,3, 5-pentanetronitrile, 1,3, 6-hexanetricarbonitrile, succinonitrile, glutaronitrile, adipodinitrile, pimelic dinitrile, suberonitrile, nonyldinitrile, decyldinitrile.
4. The nonaqueous electrolyte according to claim 1, wherein the polynitrile compound represented by the structural formula iii is selected from one or more of the following compounds:
Ethylene glycol bis (propionitrile) ether, 1, 2-propylene glycol bis (propionitrile) ether, glycerol tris (propionitrile) ether, erythritol tetrakis (propionitrile) ether, xylitol penta (propionitrile) ether, mannitol hexa (propionitrile) ether, sorbitol hexa (propionitrile) ether, galactitol hexa (propionitrile) ether.
5. The nonaqueous electrolyte according to claim 1, wherein the additive B is selected from one or more of the following compounds:
Succinonitrile, glutaronitrile, 1,3, 6-hexanedinitrile, adiponitrile, pimelic dinitrile, suberonitrile, nonodinitrile, sebaconitrile, ethylene glycol bis (propionitrile) ether, 1, 2-propanediol bis (propionitrile) ether, glycerol tris (propionitrile) ether, erythritol tetrakis (propionitrile) ether, xylitol penta (propionitrile) ether, mannitol hexa (propionitrile) ether, sorbitol hexa (propionitrile) ether, galactitol hexa (propionitrile) ether.
6. The nonaqueous electrolytic solution according to claim 1, wherein the content of the additive a is 0.05 to 10% by mass and the content of the additive B is 0.05 to 5% by mass based on 100% by mass of the total nonaqueous electrolytic solution.
7. The nonaqueous electrolytic solution according to claim 1, wherein the electrolyte salt comprises a lithium salt selected from at least one of LiPF6、LiBOB、LiDFOB、LiPO2F2、LiBF4、LiSbF6、LiAsF6、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO2F)2、LiClO4、LiAlCl4、LiCF3SO3、Li2B10Cl10、 lower aliphatic carboxylic acid lithium salts.
8. The nonaqueous electrolytic solution according to claim 7, wherein the concentration of the lithium salt is 0.1mol/L to 8mol/L.
9. A secondary battery comprising a positive electrode, a negative electrode and the nonaqueous electrolyte according to any one of claims 1 to 8.
10. The secondary battery according to claim 9, wherein the secondary battery is a lithium metal battery, a lithium ion battery, or a lithium sulfur battery.
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