CN114361593B - Electrolyte additive, lithium ion battery electrolyte and preparation method thereof, lithium ion battery and electric equipment - Google Patents
Electrolyte additive, lithium ion battery electrolyte and preparation method thereof, lithium ion battery and electric equipment Download PDFInfo
- Publication number
- CN114361593B CN114361593B CN202111653132.0A CN202111653132A CN114361593B CN 114361593 B CN114361593 B CN 114361593B CN 202111653132 A CN202111653132 A CN 202111653132A CN 114361593 B CN114361593 B CN 114361593B
- Authority
- CN
- China
- Prior art keywords
- compound
- electrolyte
- lithium ion
- ion battery
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 50
- 239000003792 electrolyte Substances 0.000 title claims abstract description 46
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 229940126062 Compound A Drugs 0.000 claims abstract description 14
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 14
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical group [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 31
- 230000000996 additive effect Effects 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- FXBLJWDJXBQLEL-UHFFFAOYSA-N ethenyl dimethyl phosphate Chemical compound COP(=O)(OC)OC=C FXBLJWDJXBQLEL-UHFFFAOYSA-N 0.000 description 2
- 125000004991 fluoroalkenyl group Chemical group 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 description 1
- ZFMOJHVRFMOIGF-UHFFFAOYSA-N 2,4,6-trimethoxy-1,3,5,2,4,6-trioxatriborinane Chemical compound COB1OB(OC)OB(OC)O1 ZFMOJHVRFMOIGF-UHFFFAOYSA-N 0.000 description 1
- GBBSAMQTQCPOBF-UHFFFAOYSA-N 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane Chemical compound CB1OB(C)OB(C)O1 GBBSAMQTQCPOBF-UHFFFAOYSA-N 0.000 description 1
- VOXXGUAZBWSUSS-UHFFFAOYSA-N 2,4,6-triphenyl-1,3,5,2,4,6-trioxatriborinane Chemical compound O1B(C=2C=CC=CC=2)OB(C=2C=CC=CC=2)OB1C1=CC=CC=C1 VOXXGUAZBWSUSS-UHFFFAOYSA-N 0.000 description 1
- WBRSYBLNSTYNPP-UHFFFAOYSA-N 2,4,6-tris(ethenyl)-1,3,5,2,4,6-trioxatriborinane Chemical compound C=CB1OB(C=C)OB(C=C)O1 WBRSYBLNSTYNPP-UHFFFAOYSA-N 0.000 description 1
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 1
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- LBZRRXXISSKCHV-UHFFFAOYSA-N [B].[O] Chemical group [B].[O] LBZRRXXISSKCHV-UHFFFAOYSA-N 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- DFJYZCUIKPGCSG-UHFFFAOYSA-N decanedinitrile Chemical compound N#CCCCCCCCCC#N DFJYZCUIKPGCSG-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical group OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Abstract
The application provides an electrolyte additive, lithium ion battery electrolyte, a preparation method of the electrolyte additive, a lithium ion battery and electric equipment. Electrolyte additives including compound a, compound B, and compound C. The lithium ion battery electrolyte comprises an electrolyte additive. The preparation method of the lithium ion battery electrolyte comprises the following steps: mixing the raw materials. The lithium ion battery includes a lithium ion battery electrolyte. According to the electrolyte additive, the compound A is a phosphorus-containing derivative, and by using a group containing unsaturated bonds, the compound A can form a film on a negative electrode to protect the negative electrode, and meanwhile, a P-O bond can combine H and metal ions to protect a positive electrode; the compound B is a boron-oxygen annular structure, inorganic film components can be increased when the compound B participates in film formation, the internal resistance of the battery can be reduced, the compound B also has a better protection effect on high voltage, and through the synergistic effect of the compounds A, B and C, the decomposition of electrolyte under high voltage can be inhibited, the internal resistance of the battery is reduced, and the comprehensive performance of the battery is obviously improved.
Description
Technical Field
The application relates to the field of lithium ion batteries, in particular to an electrolyte additive, lithium ion battery electrolyte, a preparation method of the lithium ion battery electrolyte, a lithium ion battery and electric equipment.
Background
Lithium ion secondary batteries have many advantages, but there is a need to develop suitable electrolytes to improve the high temperature and high voltage performance of the batteries. At present, commercial electrolyte is mostly composed of carbonic ester or carboxylic ester solvent, lithium hexafluorophosphate and additive, and in a high-voltage battery, the conventional electrolyte is easy to decompose due to higher voltage, so that gas is produced seriously during high-temperature circulation or storage.
In order to solve the problem, some high-temperature and high-voltage additives such as nitriles are added in the prior art, for example, CN108054431a discloses an electrolyte suitable for a fast-charging system and a lithium ion cylindrical battery containing the electrolyte, wherein the additives of the electrolyte comprise a film forming additive, a high-temperature additive and a low-temperature additive; wherein the film forming additive comprises a combination of fluoroethylene carbonate FEC, vinylene carbonate VC, succinonitrile SN and methylene methane disulfonate MMDS; the high-temperature additive is any one of 1, 3-propane sultone PS or propenyl-1, 3-sultone PST; the low-temperature additive is vinyl sulfate DTD. The electrolyte is suitable for a lithium ion cylindrical battery of a fast charge system, can obviously improve the fast charge cycle performance of the battery under high multiplying power, and has good high-low temperature performance. As another example, CN103208648A discloses an electrolyte for a flexible package lithium ion secondary battery and a battery comprising the same, wherein the electrolyte comprises an organic solvent, a lithium salt and an additive, and the additive comprises an additive a, an additive B and an additive C; the additive A is tert-amyl benzene and/or tert-butyl benzene, and the mass percentage of the additive A in the electrolyte is 5-10%; the additive B is at least one of malononitrile, succinonitrile, glutaronitrile, adiponitrile, pimelic dinitrile, suberonitrile, nondinitrile and sebaconitrile, and the mass percentage of the additive B in the electrolyte is 1-8%; the additive C is fluoroethylene carbonate, and the mass percentage of the additive C in the electrolyte is 2-10%. Compared with the prior art, the additive A, B, C is matched and used in the soft package lithium ion secondary battery with high voltage design, so that the battery can be ensured to have good cycle performance and high-temperature storage performance, and also can be ensured to have good overcharge resistance.
However, the addition of nitrile additives can result in a relatively high battery impedance, and particularly some additives are not compatible with ternary and lithium cobaltate systems, and have relatively single performance, so that a high-temperature and high-voltage electrolyte with better performance needs to be developed to be suitable for different high-voltage systems.
Disclosure of Invention
The application aims to provide an electrolyte additive, lithium ion battery electrolyte, a preparation method of the electrolyte additive, a lithium ion battery and electric equipment, so as to solve the problems.
In order to achieve the above purpose, the present application adopts the following technical scheme:
an electrolyte additive comprising a compound a, a compound B, and a compound C;
the structural general formula of the compound A is as follows:
wherein R is 1 、R 2 、R 3 Each independently is one of H, alkyl, alkenyl, alkynyl, fluoroalkyl, fluoroalkenyl, and R 1 、R 2 And R is 3 Not all H, at least one of which is alkenyl or alkynyl;
the structural general formula of the compound B is as follows:
wherein R is 4 、R 5 And R is 6 Fluoro substituents independently selected from alkyl, alkoxy, phenyl, phenoxy, alkenyl, alkynyl, and the like;
the additive C comprises at least one of vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, hexadinitrile and succinonitrile.
Preferably, the compound A comprises At least one of them.
Preferably, the compound B packageScraper
At least one of them.
The application also provides lithium ion battery electrolyte, which comprises the electrolyte additive.
Preferably, the lithium ion battery electrolyte comprises the following components in percentage by mass:
0.1% -5% of the compound A, 0.1% -5% of the compound B, 0.1% -5% of the compound C, 10% -18% of lithium salt and 67% -89.7% of organic solvent.
Preferably, the lithium salt comprises lithium hexafluorophosphate and/or lithium bis-fluorosulfonyl imide.
Preferably, the organic solvent includes at least one of ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, ethylmethyl carbonate, propyl propionate and ethyl propionate.
The application also provides a preparation method of the lithium ion battery electrolyte, which comprises the following steps:
mixing the raw materials.
The application also provides a lithium ion battery, which comprises the lithium ion battery electrolyte.
The application also provides electric equipment, which comprises the lithium ion battery.
Compared with the prior art, the beneficial effects of this application include:
according to the electrolyte additive, the compound A is a phosphorus-containing derivative, and by using a group containing unsaturated bonds, the compound A can form a film on a negative electrode to protect the negative electrode, and meanwhile, a P-O bond can combine H and metal ions to protect a positive electrode; the compound B is a boron-oxygen ring structure, and when the compound B participates in film formation, inorganic film components can be increased, the internal resistance of the battery can be reduced, the compound B has a better protection effect on high voltage, and through the synergistic effect of the compound A, the compound B and the compound C, the decomposition of electrolyte under high voltage can be inhibited, the internal resistance of the battery can be reduced, and the comprehensive performance of the battery can be obviously improved.
According to the lithium ion battery electrolyte, the battery impedance is reduced through the cooperation of the compound A, the compound B, the compound C, the lithium salt and the organic solvent in the electrolyte additive, and the lithium ion battery electrolyte can be effectively compatible with high-temperature and high-voltage systems such as ternary lithium ion batteries, lithium cobaltate batteries and the like.
The lithium ion battery and the electric equipment provided by the application are excellent in electrical performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
Fig. 1 is a 500 cycle curve of a lithium ion battery prepared by the electrolyte additives provided in example 3 and comparative example 1.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
An electrolyte additive comprising a compound a, a compound B, and a compound C;
the structural general formula of the compound A is as follows:
wherein the method comprises the steps of，R 1 、R 2 、R 3 Each independently is one of H, alkyl, alkenyl, alkynyl, fluoroalkyl, fluoroalkenyl, and R 1 、R 2 And R is 3 Not all H, at least one of which is alkenyl or alkynyl;
the structural general formula of the compound B is as follows:
wherein R is 4 、R 5 And R is 6 Fluoro substituents independently selected from alkyl, alkoxy, phenyl, phenoxy, alkenyl, alkynyl, and the like;
the additive C comprises at least one of vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, hexadinitrile and succinonitrile.
In an alternative embodiment, the compound a comprises(dimethyl-vinyl phosphate), a method of preparing the same, and a method of preparing the same>(dimethyl ethynyl phosphonate) and +.>At least one of (1-fluorovinylphosphonic acid dimethyl ester).
In an alternative embodiment, the compound B comprises
(trimethylboroxine),(trimethoxyboroxine),(Triphenoxy boroxine),
(2, 4, 6-Trivinylboroxine),(2, 4, 6-tris (3, 4, 5-trifluorobenzene) boroxine) and +.>(phenylboronic anhydride).
The application also provides lithium ion battery electrolyte, which comprises the electrolyte additive.
In an alternative embodiment, the lithium ion battery electrolyte comprises, in mass percent:
0.1% -5% of the compound A, 0.1% -5% of the compound B, 0.1% -5% of the compound C, 10% -18% of lithium salt and 67% -89.7% of organic solvent.
Alternatively, the content of the compound a in the lithium ion battery electrolyte may be any value between 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and 0.1% -5%; the content of the compound B may be any value between 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and 0.1% -5%; the content of the compound C may be any value between 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and 0.1% -5%; the content of lithium salt may be any value between 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% and 10% -18%; the organic solvent may be present in an amount of any of 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 89.7%, and 67% -89.7%.
In an alternative embodiment, the lithium salt comprises lithium hexafluorophosphate and/or lithium bis-fluorosulfonyl imide.
In an alternative embodiment, the organic solvent includes at least two of ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, methylethyl carbonate, propyl propionate, and ethyl propionate.
The application also provides a preparation method of the lithium ion battery electrolyte, which comprises the following steps:
mixing the raw materials.
The application also provides a lithium ion battery, which comprises the lithium ion battery electrolyte.
The application also provides electric equipment, which comprises the lithium ion battery.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The compounds used in the examples are first described:
compound a used the following structure:
compound B used the following structure:
compounds A1 and B2 were purchased from Alatine, a reagent net, and B1 was purchased from Mobel chemical net; the rest compounds are self-made, and the preparation method is as follows:
the synthesis equation for compound A2 is:
the preparation method comprises the following steps:
mixing dimethyl-vinyl phosphate and bromine in a closed container according to a ratio of 1:1, maintaining the temperature at 25-40 ℃, stirring for 1h to obtain an intermediate product (a), heating the intermediate product (a) in an absolute potassium hydroxide ethanol solution for 2h, evaporating to remove ethanol, crystallizing at a low temperature, and filtering to obtain the ethynyl dimethyl phosphonate.
The characterization results of the obtained materials were as follows:
the synthesis equation for compound A3 is:
the preparation method comprises the following steps:
and adding dimethyl ethynyl phosphonate and a catalyst into a closed steel cylinder, keeping the temperature at 25-40 ℃, and introducing a certain amount of HF gas to obtain the dimethyl 1-fluorovinyl phosphonate.
The characterization results of the obtained materials were as follows:
the synthesis equation for compound B3 is:
the preparation method comprises the following steps:
dissolving triphenyl borate in toluene solution, heating to 80 ℃ under the condition of a catalyst, maintaining for 1h, and removing volatile matters by vacuum distillation at 80 ℃ to obtain the triphenoxyboroxine.
Examples 1 to 8
Examples 1-8 provide an electrolyte additive and lithium ion battery electrolyte with the formulation shown in table 1 below:
table 1 example formulation table
The amount of the organic solvent used in table 1 was 100% minus the balance of the lithium salt electrolyte, compound a, compound B, and compound C.
Comparative examples 1 to 4
In order to illustrate the effects of the electrolyte additives provided herein and the components in the lithium ion battery electrolyte, comparative examples 1-4 are specifically provided for comparison, and the specific formulations are shown in table 2 below:
table 2 comparative example formulation table
/>
The amount of the organic solvent used in table 2 was 100% minus the balance of the lithium salt electrolyte, compound a, compound B, and compound C.
And (3) performance detection:
(1) Cycle performance experiment: the batteries obtained in each example and comparative example were tested for cycle performance of charge and discharge at a rate of 3.0 to 4.35/4.4v and 1c at room temperature and 45 c, respectively, and the capacity retention rate was recorded for 500 weeks in cycles. Fig. 1 is a 500 cycle curve of a lithium ion battery prepared by the electrolyte additives provided in example 3 and comparative example 1.
(2) High temperature storage experiment: the batteries obtained in each of examples and comparative examples were subjected to a charge-discharge cycle test 5 times at a charge-discharge rate of 1C at room temperature, and then the 1C rate was charged to a full-charge state. The 1C capacity Q and the battery thickness T are recorded separately. Storing the battery in full state at 60deg.C for 7 days, and recording battery thickness T 0 And 1C discharge capacity Q 1 The battery was then charged and discharged at 1C for 5 weeks at room temperature, and the 1C discharge capacity Q was recorded 2 And cell thickness T 1 Experimental data such as the high-temperature storage capacity retention rate, the capacity recovery rate, the thickness expansion rate and the like of the battery are obtained through calculation, the recording results are shown in table 3, and the following formula is adopted for calculation:
capacity retention (%) =q 1 (mAh)÷Q(mAh)×100％
Capacity recovery (%) =q 2 (mAh)÷Q(mAh)×100％
Thickness expansion ratio (%) = (T) 1 -T 0 )÷T 0 ×100％。
(3) Low temperature discharge experiment: the batteries obtained in each example and comparative example were cycled 3 times at room temperature at a rate of 0.5C charge and 0.2C discharge, then charged to a full charge state at a rate of 0.5C, and the discharge capacity Q of the last time was recorded 3 Placing the battery in a full-charge state in a comprehensive test temperature cabinet at-20 ℃, standing for 4 hours, discharging to 3V at 0.2C multiplying power, and recording the discharge capacity Q 4 。
Low-temperature discharge capacity retention (%) =q 4 /Q 3 ×100％。
The test results are shown in table 3:
table 3 test results
/>
As can be seen from table 3: the normal temperature cycle performance and the high temperature cycle performance of the lithium secondary battery using the electrolyte are obviously improved, and the high temperature storage flatulence of the battery is also obviously improved.
It is apparent from examples 1 to 5 and comparative examples 1 to 4 that both additive A and additive B have improved performance for high voltage batteries and the improvement effect has effects on lithium cobaltate and ternary. The effect of the additive A, B, C is better than that of the additive alone, which indicates that the ABC has synergistic effect.
It is understood from comparison of example 5 and example 6 that the content of additive a is small and the effect of improving the cycle performance of the lithium secondary battery is not significant.
As is clear from a comparison between example 5 and example 7, the content of additive A is too high, which is detrimental to the low-temperature discharge performance of the battery, and the normal-temperature and high-temperature cycle performance is also somewhat lowered.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (9)
1. An electrolyte additive, characterized by comprising a compound A, a compound B and a compound C;
the compound A comprises、/>And->At least one of (a) and (b);
the structural general formula of the compound B is as follows:
；
wherein R is 4 、R 5 And R is 6 Each independently selected from the group consisting of alkyl, alkoxy, phenyl, phenoxy, alkenyl, alkynyl, and fluoro substituents thereof;
the compound C comprises at least one of vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, hexadinitrile and succinonitrile.
2. The electrolyte additive according to claim 1, wherein the compound B comprises、/>、/>、/>、And->At least one of them.
3. A lithium ion battery electrolyte characterized in that the raw materials thereof comprise the electrolyte additive as claimed in claim 1 or 2.
4. The lithium ion battery electrolyte according to claim 3, wherein the raw materials comprise, in mass percent:
0.1% -5% of the compound A, 0.1% -5% of the compound B, 0.1% -5% of the compound C, 10% -18% of lithium salt and 67% -89.7% of organic solvent.
5. The lithium ion battery electrolyte of claim 4, wherein the lithium salt comprises lithium hexafluorophosphate and/or lithium bis-fluorosulfonyl imide.
6. The lithium ion battery electrolyte of claim 4 or 5, wherein the organic solvent comprises at least one of ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, methylethyl carbonate, propyl propionate, and ethyl propionate.
7. A method for preparing the lithium ion battery electrolyte according to any one of claims 3 to 6, comprising:
mixing the raw materials.
8. A lithium ion battery comprising the lithium ion battery electrolyte of any one of claims 3-6.
9. A powered device comprising the lithium-ion battery of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111653132.0A CN114361593B (en) | 2021-12-30 | 2021-12-30 | Electrolyte additive, lithium ion battery electrolyte and preparation method thereof, lithium ion battery and electric equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111653132.0A CN114361593B (en) | 2021-12-30 | 2021-12-30 | Electrolyte additive, lithium ion battery electrolyte and preparation method thereof, lithium ion battery and electric equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114361593A CN114361593A (en) | 2022-04-15 |
| CN114361593B true CN114361593B (en) | 2024-03-19 |
Family
ID=81103440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111653132.0A Active CN114361593B (en) | 2021-12-30 | 2021-12-30 | Electrolyte additive, lithium ion battery electrolyte and preparation method thereof, lithium ion battery and electric equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114361593B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111211354A (en) * | 2020-01-15 | 2020-05-29 | 松山湖材料实验室 | High-voltage lithium ion battery combined electrolyte additive, electrolyte and battery thereof |
| CN111682264A (en) * | 2020-06-05 | 2020-09-18 | 惠州锂威新能源科技有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
| CN112820941A (en) * | 2019-11-15 | 2021-05-18 | 浙江中蓝新能源材料有限公司 | Composition for electrolyte |
| CN113169395A (en) * | 2019-01-04 | 2021-07-23 | 国立研究开发法人物质·材料研究机构 | Electrolyte for lithium-air battery and lithium-air battery using same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3113274B1 (en) * | 2014-02-25 | 2020-09-30 | Mitsubishi Chemical Corporation | Non-aqueous electrolytic solution and non-aqueous electrolyte secondary battery using same |
-
2021
- 2021-12-30 CN CN202111653132.0A patent/CN114361593B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113169395A (en) * | 2019-01-04 | 2021-07-23 | 国立研究开发法人物质·材料研究机构 | Electrolyte for lithium-air battery and lithium-air battery using same |
| CN112820941A (en) * | 2019-11-15 | 2021-05-18 | 浙江中蓝新能源材料有限公司 | Composition for electrolyte |
| CN111211354A (en) * | 2020-01-15 | 2020-05-29 | 松山湖材料实验室 | High-voltage lithium ion battery combined electrolyte additive, electrolyte and battery thereof |
| CN111682264A (en) * | 2020-06-05 | 2020-09-18 | 惠州锂威新能源科技有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 提高锂离子电池安全性能的添加剂的进展;邢桃峰;仇卫华;连芳;于昭新;;电池;20091025(05);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114361593A (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105845983B (en) | Electrolyte and lithium ion battery containing same | |
| CN105826606B (en) | Electrolyte and lithium ion battery containing same | |
| CN109687021B (en) | High-temperature-resistant non-aqueous electrolyte for lithium ion battery | |
| CN111244546B (en) | Electrolyte for lithium ion battery suitable for quick charging and lithium ion battery | |
| CN108539270B (en) | Lithium secondary battery electrolyte and lithium secondary battery thereof | |
| CN107210489B (en) | Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery | |
| CN111129586A (en) | High-voltage lithium cobalt oxide lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN111525192A (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| JP2019536193A (en) | Non-aqueous electrolyte for lithium ion battery and lithium ion battery | |
| CN114142090B (en) | Electrolyte additive composition, electrolyte and lithium secondary battery | |
| CN114361593B (en) | Electrolyte additive, lithium ion battery electrolyte and preparation method thereof, lithium ion battery and electric equipment | |
| CN115441057A (en) | Electrolyte and battery comprising same | |
| CN115621555A (en) | Non-aqueous electrolyte and lithium ion battery | |
| WO2023020314A1 (en) | Non-aqueous electrolyte solution and lithium battery | |
| CN112271327B (en) | Electrolyte solution, and electrochemical device and electronic device containing the same | |
| WO2023159799A1 (en) | Electrolyte additive, non-aqueous electrolyte and lithium ion battery | |
| CN117096447A (en) | Battery cell | |
| CN112490503A (en) | Electrolyte additive, electrolyte and lithium ion battery | |
| CN114122521B (en) | Nonaqueous electrolyte for lithium ion battery and lithium ion battery comprising same | |
| CN112151864B (en) | Electrolyte solution, and electrochemical device and electronic device comprising same | |
| CN117276660A (en) | Electrolyte additive, lithium ion battery electrolyte and lithium ion battery | |
| CN116130764A (en) | Electrolyte and battery | |
| CN116404248A (en) | Overcharge-preventing electrolyte and lithium ion battery comprising same | |
| CN117673467A (en) | Electrolyte and battery comprising same | |
| CN116759643A (en) | Electrolyte and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |