CN103219543A - Electrolyte for lithium battery and lithium ion battery comprising same - Google Patents
Electrolyte for lithium battery and lithium ion battery comprising same Download PDFInfo
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- CN103219543A CN103219543A CN2013101503395A CN201310150339A CN103219543A CN 103219543 A CN103219543 A CN 103219543A CN 2013101503395 A CN2013101503395 A CN 2013101503395A CN 201310150339 A CN201310150339 A CN 201310150339A CN 103219543 A CN103219543 A CN 103219543A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 70
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 46
- 239000000654 additive Substances 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 32
- -1 sulfone compound Chemical class 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010439 graphite Substances 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 239000010452 phosphate Substances 0.000 claims description 15
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 14
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 9
- 239000007784 solid electrolyte Substances 0.000 abstract description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 239000012453 solvate Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 238000010998 test method Methods 0.000 description 14
- 229910013188 LiBOB Inorganic materials 0.000 description 12
- 229910013870 LiPF 6 Inorganic materials 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 8
- 239000008187 granular material Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 3
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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
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- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte for a lithium battery and a lithium ion battery comprising the same and belongs to the technical field of lithium ion batteries, and the lithium ion battery can be used for solving the problems of poor cycling performance and the like of an existing lithium ion battery. The invention provides an electrolyte used for a lithium battery and comprising a dissolvant, lithium salt and an additive, wherein the additive belongs to a sulfone compound. The sulfone compound serving as the additive is added to the electrolyte, so as to prevent a part of the electrolyte from being decomposed, so that the electrolyte has more stable electrochemical performance, and can ensure good cycle performance and excellent storage performance of the battery. In addition, the reduction potential of the cathode, positioned in the electrolyte, of the sulfone compound is about 1.0-1.5V and is lower than corresponding sulfite reduction potential, but higher than that of carbonic ester reduction potential. The sulfone compound, antecedent to solvate lithium ion intercalation, forms a film on a negative electrode interface (such as graphite) and can be used for improving the compatibility between a negative electrode and the electrolyte, and the formed solid electrolyte interface (SEI) film at the surface of the electrode is more stable.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of electrolyte for lithium cells and contain the lithium ion battery of this electrolyte.
Background technology
Lithium ion battery is because its energy density height, and good cycle and be subjected to people's attention over nearly 20 years, has obtained development at full speed.Become the leading supporting power supply of portable type electronic products such as mobile phone, digital camera and notebook computer.At present, the application of lithium ion battery expands to again on mine lamp, electric tool, electric bicycle, electric automobile, family expenses and the power station energy-storage battery.In above-mentioned application, lithium ion battery often needs to store, shelve, and is the same with other secondary cell, stores and shelve capacity, the high rate performance decay that can cause lithium ion battery.
The worsening of battery performance in the storage process mainly is that the positive pole of battery is affected.The decay main cause is that the part electrolyte decomposes generation HF, with the positive electrode active materials reaction, generates the contour resistance material of LiF on the surface.At present the main path that solves coats for positive electrode being carried out surface, and reduce HF and contact with the direct of positive electrode, or interpolation metal oxide (or hydroxide) additive that can react with HF.Also have and set about improvedly from the electrolyte aspect, this also is one of the simplest mode.Therefore, be necessary to develop a kind of new electrolyte, to guarantee battery in long term storage, capacity does not have bigger decay.
Summary of the invention
The objective of the invention is to solve the problem of capacity attenuation in storage of existing lithium ion battery, a kind of electrolyte for lithium cells of the battery capacity conservation rate that can improve is provided.
The technical scheme that solution the technology of the present invention problem is adopted is a kind of electrolyte for lithium cells, comprises solvent, lithium salts and additive, and described additive comprises sulfone compound.
Sulfone compound joins the decomposition that can prevent part electrolyte in the electrolyte effectively as additive, so the chemical property of electrolyte is more stable, can guarantee the cycle characteristics and the storge quality of battery.And the about 1.0～1.5V of cathodic reduction current potential in electrolyte of sulfone compound, be lower than corresponding sulfite reduction potential, but be higher than common carbonic ester reduction potential, also can be prior to solvation lithium ion inlay in negative pole (for example graphite) interface film forming, improve the compatibility of negative pole and electrolyte, and electrode surface solid electrolyte interface (SEI) film that forms is also more stable.
Wherein, electrolyte for lithium cells of the present invention can obtain by each raw material is directly mixed.
Preferably, described sulfone compound is methyl-sulfoxide, butyl sulfoxide, second methyl sulfoxide, 3,3, any one or a few in 3-trifluoro propyl sulfoxide, the sulfolane.
Preferably, the mass fraction of described sulfone compound is 0.01%-10%, and wherein, the mass fraction of sulfone compound is the mass fraction with respect to the quality sum of solvent and additive.
Preferably, the mass fraction of described solvent is 90.00%-99.99%, and wherein, the mass fraction of solvent is the mass fraction with respect to the quality sum of solvent and additive.
Preferably, described solvent is selected from any one or a few in ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester and the fluorinated ethylene carbonate.
Preferably, the amount of substance concentration of described lithium salts is 0.5mol/L-1.2mol/L.
Further preferably, described lithium salts is lithium hexafluoro phosphate and/or dioxalic acid lithium borate.
Select the low viscous solvent of high-k in the technique scheme, with the effective dissolving of lithium salts and the stable formation of electrode surface solid electrolyte interface (SEI) film in the assurance electrolyte.
The present invention solves to deal with problems and also comprises, at problems such as existing lithium ion battery cycle performance differences, provides a kind of lithium ion battery of good cycle.
Solving the technical scheme that the problems referred to above of the present invention adopted is a kind of lithium ion battery, comprises positive electrode, negative material and electrolyte, and described electrolyte is above-mentioned electrolyte for lithium cells.
Preferably described positive electrode is made up of the material of following mass fraction: the LiFePO4 of 91%-94%, and the conductive agent of 2-4%, the Kynoar of 4-5%, described mass fraction are the mass fractions with respect to the positive electrode gross mass;
Described negative material is made up of the material of following mass fraction: the graphite of 92%-94%, the polyacrylic acid of 6-8%, described mass fraction are the mass fractions with respect to the negative material gross mass.
Further preferably, described conductive agent is made up of in conductive black, graphite powder, carbon fiber and the carbon nano-tube one or more.
The preferred granule conductive black of conductive black in the such scheme (commodity are called supper-P), the preferred big coccolith ink powder (commodity are called KS-6) of graphite powder, the carbon fiber of the preferred commodity of carbon fiber VGCF by name.
Because the lithium ion battery that provides of the present invention has used above-mentioned electrolyte, form and stablize complete solid electrolyte membrane (SEI film), stoped electrolytical decomposition effectively, guaranteed the cycle characteristics and the storge quality of battery.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, the present invention is described in further detail below in conjunction with embodiment.
Comparative Examples
This Comparative Examples provides a kind of lithium ion battery.
The composition of the positive electrode of lithium ion battery (is 100% in the positive electrode mass fraction): 93% LiFePO4,3% carbon nano-tube, 4% Kynoar.
The composition of the negative material of lithium ion battery (is 100% in the negative material mass fraction): 94% graphite, 6% polyacrylic acid.
The composition of electrolyte (the quality sum in solvent and additive is 100%): solvent is: 25% diethyl carbonate (DEC), 37% ethyl-methyl carbonic ester (EMC), 35% fluorinated ethylene carbonate (FEC);
Additive is: 3% propylene sulfite;
Electrolytic salt is: lithium hexafluoro phosphate LiPF
6With dioxalic acid lithium borate LiBOB, wherein lithium hexafluoro phosphate LiPF
6Amount of substance concentration in electrolyte is 0.4mol/L, and the amount of substance concentration of dioxalic acid lithium borate LiBOB in electrolyte is 0.6mol/L.
The preparation method of battery:
Anodal preparation: according to above-mentioned each raw material of anode formula weighing, be dispersed in N-N-methyl-2-2-pyrrolidone N-(NMP) solution, be prepared into anodal mixed slurry, and slurry is coated on the positive electrical adfluxion fluid aluminium foil, obtain anode pole piece through after the dry roll-in.
Negative pole preparation: according to above-mentioned each raw material of cathode formula weighing, be dispersed in N-N-methyl-2-2-pyrrolidone N-(NMP) solution, be prepared into the mixed slurry of negative pole, and slurry is coated on the cathodal current collector aluminium foil, obtain cathode pole piece through after the dry roll-in.
The preparation of electrolyte: by above-mentioned each raw material of electrolyte prescription weighing, mix, be mixed with electrolyte.
With positive plate, negative plate and electrolyte and other necessary battery component of the lithium ion battery of above-mentioned preparation, for example, barrier film (celgard2400 film) and shell etc. are assembled into 18650 type batteries.
Battery to the preparation of this Comparative Examples carries out the charge/discharge capacity test: at first, at normal temperatures, 18650 type batteries of this Comparative Examples preparation are implemented the charging and twice circulation (0.5C) of discharging, record is the discharge capacity C of circulation for the second time
2, be the discharge capacity before storing.Battery was shelved 3 months with charged state normal temperature again, implemented discharge (0.5C) afterwards at normal temperatures, the gained discharge capacity is designated as C
3Last calculated capacity conservation rate=C
3/ C
2The results are shown in Table 1.
Embodiment 1:
Present embodiment provides a kind of lithium ion battery.
The composition of the positive electrode of lithium ion battery (is 100% in the positive electrode mass fraction): 93% LiFePO4,3% carbon nano-tube, 4% Kynoar.
The composition of the negative material of lithium ion battery (is 100% in the negative material mass fraction): 94% graphite, 6% polyacrylic acid.
The composition of electrolyte (the quality sum in solvent and additive is 100%): solvent is: 25% diethyl carbonate (DEC), 39.99% ethyl-methyl carbonic ester (EMC), 35% fluorinated ethylene carbonate (FEC);
Additive is: 0.01% (DMSO);
Electrolytic salt is: lithium hexafluoro phosphate LiPF
6With dioxalic acid lithium borate LiBOB, wherein lithium hexafluoro phosphate LiPF
6Amount of substance concentration in electrolyte is 0.4mol/L, and the amount of substance concentration of dioxalic acid lithium borate LiBOB in electrolyte is 0.6mol/L.
The preparation method of battery: identical with the preparation method of battery in the Comparative Examples.
Battery to the present embodiment preparation carries out the charge/discharge capacity test: method of testing is identical with the charge/discharge capacity method of testing of the battery of Comparative Examples, and test result sees Table 1.
As seen, with respect to Comparative Examples sulfone compound is joined the decomposition that can prevent part electrolyte in the electrolyte effectively as additive, so the chemical property of electrolyte is more stable, can guarantees the cycle characteristics and the storge quality of battery.And the about 1.0～1.5V of cathodic reduction current potential in electrolyte of sulfone compound, be lower than corresponding sulfite reduction potential, but be higher than common carbonic ester reduction potential, also can be prior to solvation lithium ion inlay in negative pole (for example graphite) interface film forming, improve the compatibility of negative pole and electrolyte, and electrode surface solid electrolyte interface (SEI) film that forms is also more stable.
Table 1 is the capability retention of battery in the embodiment of the invention
Embodiment 2:
Present embodiment provides a kind of lithium ion battery.
The composition of the positive electrode of lithium ion battery (is 100% in the positive electrode mass fraction): 94% LiFePO4,2% carbon fiber, 4% Kynoar.
The composition of the negative material of lithium ion battery (is 100% in the negative material mass fraction): 92% graphite, 8% polyacrylic acid.
The composition of electrolyte (the quality sum in solvent and additive is 100%): solvent is: 41% diethyl carbonate (DEC), 58% ethyl-methyl carbonic ester (EMC);
Additive is: 0.5% methyl-sulfoxide (DMSO) and 0.5% butyl sulfoxide;
Electrolytic salt is: lithium hexafluoro phosphate LiPF
6, its amount of substance concentration in electrolyte is 1.2mol/L.
The preparation method of battery: identical with the preparation method of battery in the Comparative Examples.
Battery to the present embodiment preparation carries out the charge/discharge capacity test: method of testing is identical with the charge/discharge capacity method of testing of the battery of Comparative Examples, and test result sees Table 1.
Embodiment 3:
Present embodiment provides a kind of lithium ion battery.
The composition of the positive electrode of lithium ion battery (is 100% in the positive electrode mass fraction): 91% LiFePO4,4% granule conductive black, 5% Kynoar.
The composition of the negative material of lithium ion battery (is 100% in the negative material mass fraction): 93% graphite, 7% polyacrylic acid.
The composition of electrolyte (the quality sum in solvent and additive is 100%): solvent is: 32% ethylene carbonate (EC), 30% diethyl carbonate (DEC), 35% fluorinated ethylene carbonate (FEC);
Additive is: 1% methyl-sulfoxide (DMSO), 1% butyl sulfoxide, 1% second methyl sulfoxide (EMS);
Electrolytic salt is: lithium hexafluoro phosphate LiPF
6, lithium hexafluoro phosphate LiPF wherein
6Amount of substance concentration in electrolyte is 0.5mol/L.
The preparation method of battery: identical with the preparation method of battery in the Comparative Examples.
Battery to the present embodiment preparation carries out the charge/discharge capacity test: method of testing is identical with the charge/discharge capacity method of testing of the battery of Comparative Examples, and test result sees Table 1.
Embodiment 4:
Present embodiment provides a kind of lithium ion battery.
The composition of the positive electrode of lithium ion battery (is 100% in the positive electrode mass fraction): 92% LiFePO4,2% carbon nano-tube and 2% carbon fiber, 4% Kynoar.
The composition of the negative material of lithium ion battery (is 100% in the negative material mass fraction): 91% graphite, 9% polyacrylic acid.
The composition of electrolyte (the quality sum in solvent and additive is 100%): solvent is: 25% ethylene carbonate (EC), 30% dimethyl carbonate (DMC), 35% ethyl-methyl carbonic ester (EMC);
Additive is: 10% 3,3,3-trifluoro propyl sulfoxide (FPMS);
Electrolytic salt is: dioxalic acid lithium borate LiBOB, wherein the amount of substance concentration of dioxalic acid lithium borate LiBOB in electrolyte is 0.6mol/L.
The preparation method of battery: identical with the preparation method of battery in the Comparative Examples.
Battery to the present embodiment preparation carries out the charge/discharge capacity test: method of testing is identical with the charge/discharge capacity method of testing of the battery of Comparative Examples, and test result sees Table 1.
Embodiment 5:
Present embodiment provides a kind of lithium ion battery.
The composition of the positive electrode of lithium ion battery (is 100% in the positive electrode mass fraction): 91% LiFePO4,4% granule conductive black, 5% Kynoar.
The composition of the negative material of lithium ion battery (is 100% in the negative material mass fraction): 92% graphite, 8% polyacrylic acid.
The composition of electrolyte (the quality sum in solvent and additive is 100%): solvent is: 55% diethyl carbonate (DEC), 41% fluorinated ethylene carbonate (FEC);
Additive is: 1% methyl-sulfoxide (DMSO), 3% second methyl sulfoxide (EMS);
Electrolytic salt is: lithium hexafluoro phosphate LiPF
6With dioxalic acid lithium borate LiBOB, wherein lithium hexafluoro phosphate LiPF
6Amount of substance concentration in electrolyte is 0.5mol/L, and the amount of substance concentration of dioxalic acid lithium borate LiBOB in electrolyte is 0.4mol/L.
Battery to the present embodiment preparation carries out the charge/discharge capacity test: method of testing is identical with the charge/discharge capacity method of testing of the battery of Comparative Examples, and test result sees Table 1.
Embodiment 6:
Present embodiment provides a kind of lithium ion battery.
The composition of the positive electrode of lithium ion battery (is 100% in the positive electrode mass fraction): 91% LiFePO4,4% granule conductive black, 5% Kynoar.
The composition of the negative material of lithium ion battery (is 100% in the negative material mass fraction): 94% graphite, 6% polyacrylic acid.
The composition of electrolyte (the quality sum in solvent and additive is 100%): solvent is: 33% ethylene carbonate (EC), 31% diethyl carbonate (DEC), 31% fluorinated ethylene carbonate (FEC);
Additive is: 2% butyl sulfoxide, 3% 3,3,3-trifluoro propyl sulfoxide (FPMS);
Electrolytic salt is: lithium hexafluoro phosphate LiPF
6With dioxalic acid lithium borate LiBOB, wherein lithium hexafluoro phosphate LiPF
6Amount of substance concentration in electrolyte is 0.4mol/L, and the amount of substance concentration of dioxalic acid lithium borate LiBOB in electrolyte is 0.4mol/L.
Battery to the present embodiment preparation carries out the charge/discharge capacity test: method of testing is identical with the charge/discharge capacity method of testing of the battery of Comparative Examples, and test result sees Table 1.
Embodiment 7:
Present embodiment provides a kind of lithium ion battery.
The composition of the positive electrode of lithium ion battery (is 100% in the positive electrode mass fraction): 92% LiFePO4,3% granule conductive black, 5% Kynoar.
The composition of the negative material of lithium ion battery (is 100% in the negative material mass fraction): 93% graphite, 7% polyacrylic acid.
The composition of electrolyte (the quality sum in solvent and additive is 100%): solvent is: 61% ethylene carbonate (EC), 31% fluorinated ethylene carbonate (FEC);
Additive is: 8% sulfolane;
Electrolytic salt is: lithium hexafluoro phosphate LiPF
6With dioxalic acid lithium borate LiBOB, wherein lithium hexafluoro phosphate LiPF
6Amount of substance concentration in electrolyte is 0.5mol/L, and the amount of substance concentration of dioxalic acid lithium borate LiBOB in electrolyte is 0.6mol/L.
The preparation method of battery: identical with the preparation method of battery in the Comparative Examples.
Battery to the present embodiment preparation carries out the charge/discharge capacity test: method of testing is identical with the charge/discharge capacity method of testing of the battery of Comparative Examples, and test result sees Table 1.
Because the lithium ion battery that provides of the present invention has used above-mentioned electrolyte, complete solid electrolyte membrane (SEI film) is stablized in formation, stoped electrolytical decomposition effectively, guaranteed the cycle characteristics and the storge quality of battery, the capability retention of battery is more than 97.65%.
Be understandable that, improved the cycle characteristics and the storge quality of battery as additive, just belong to protection scope of the present invention as long as added sulfone compound in the electrolyte of battery.Wherein, additive of the kind of solvent types and content, lithium salts and content, other kind (for example can be ethyl sulfate, propylene sulfite etc.) and content all can be selected from prior art.Certainly, the positive electrode of above-mentioned battery also can select from prior art, for example, positive electrode can be lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide etc.
Be understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement also are considered as protection scope of the present invention.
Claims (10)
1. an electrolyte for lithium cells comprises solvent, lithium salts and additive, it is characterized in that, described additive comprises sulfone compound.
2. electrolyte for lithium cells as claimed in claim 1 is characterized in that, described sulfone compound is methyl-sulfoxide, butyl sulfoxide, second methyl sulfoxide, 3,3, any one or a few in 3-trifluoro propyl sulfoxide, the sulfolane.
3. electrolyte for lithium cells as claimed in claim 1 is characterized in that, the mass fraction of described sulfone compound is 0.01%-10%, and wherein, the mass fraction of sulfone compound is the mass fraction with respect to the quality sum of solvent and additive.
4. electrolyte for lithium cells as claimed in claim 1 is characterized in that, the mass fraction of described solvent is 90.00%-99.99%, and wherein, the mass fraction of solvent is the mass fraction with respect to the quality sum of solvent and additive.
5. electrolyte for lithium cells as claimed in claim 1 is characterized in that, described solvent is selected from any one or a few in ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester and the fluorinated ethylene carbonate.
6. electrolyte for lithium cells as claimed in claim 1 is characterized in that, the amount of substance concentration of described lithium salts is 0.5mol/L-1.2mol/L.
7. electrolyte for lithium cells as claimed in claim 5 is characterized in that, described lithium salts is lithium hexafluoro phosphate and/or dioxalic acid lithium borate.
8. a lithium battery comprises positive electrode, negative material and electrolyte, it is characterized in that, described electrolyte is any described electrolyte for lithium cells of claim 1-7.
9. lithium battery as claimed in claim 8 is characterized in that,
Described positive electrode is made up of the material of following mass fraction: the LiFePO4 of 91%-94%, and the conductive agent of 2-4%, the Kynoar of 4-5%, described mass fraction are the mass fractions with respect to the positive electrode gross mass;
Described negative material is made up of the material of following mass fraction: the graphite of 92%-94%, the polyacrylic acid of 6-8%, described mass fraction are the mass fractions with respect to the negative material gross mass.
10. lithium battery as claimed in claim 9 is characterized in that, described conductive agent is made up of in conductive black, graphite powder, carbon fiber and the carbon nano-tube one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101503395A CN103219543A (en) | 2013-04-26 | 2013-04-26 | Electrolyte for lithium battery and lithium ion battery comprising same |
Applications Claiming Priority (1)
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| CN103531845A (en) * | 2013-10-24 | 2014-01-22 | 兰州理工大学 | Lithium-ion battery electrolyte taking LiBF2SO4 as basic lithium salt |
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| CN105895958A (en) * | 2016-06-29 | 2016-08-24 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
| CN105958120A (en) * | 2016-06-28 | 2016-09-21 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery using same |
| CN106797022A (en) * | 2014-10-15 | 2017-05-31 | 学校法人东京理科大学 | The binding agent of potassium ion secondary battery cathode or potassium ion capacitor negative pole, potassium ion secondary cell or potassium ion capacitor and potassium ion secondary battery negative pole use or potassium ion capacitor anode |
| CN107706456A (en) * | 2016-08-08 | 2018-02-16 | 中国电子科技集团公司第十八研究所 | Lithium fluorocarbon battery electrolyte of mixed solvent containing dimethyl sulfoxide and preparation method thereof |
| CN108110321A (en) * | 2017-12-27 | 2018-06-01 | 河南省法恩莱特新能源科技有限公司 | A kind of lithium battery high-voltage electrolyte |
| CN109273763A (en) * | 2018-09-06 | 2019-01-25 | 贵州兴锂新能源科技有限公司 | It is a kind of using lithium titanate as the lithium-ion battery electrolytes of cathode |
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| CN103531845A (en) * | 2013-10-24 | 2014-01-22 | 兰州理工大学 | Lithium-ion battery electrolyte taking LiBF2SO4 as basic lithium salt |
| CN106797022A (en) * | 2014-10-15 | 2017-05-31 | 学校法人东京理科大学 | The binding agent of potassium ion secondary battery cathode or potassium ion capacitor negative pole, potassium ion secondary cell or potassium ion capacitor and potassium ion secondary battery negative pole use or potassium ion capacitor anode |
| CN105428711A (en) * | 2014-10-24 | 2016-03-23 | 山东鸿正电池材料科技有限公司 | Electrolyte solution of lithium manganate battery used at high temperature |
| CN105958120A (en) * | 2016-06-28 | 2016-09-21 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery using same |
| CN105958120B (en) * | 2016-06-28 | 2019-05-21 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery using same |
| CN105895957A (en) * | 2016-06-29 | 2016-08-24 | 宁德时代新能源科技股份有限公司 | Battery fluid and lithium ion battery |
| CN105895958A (en) * | 2016-06-29 | 2016-08-24 | 宁德时代新能源科技股份有限公司 | Electrolyte and lithium ion battery |
| CN105895957B (en) * | 2016-06-29 | 2019-04-02 | 宁德时代新能源科技股份有限公司 | Battery fluid and lithium ion battery |
| CN107706456A (en) * | 2016-08-08 | 2018-02-16 | 中国电子科技集团公司第十八研究所 | Lithium fluorocarbon battery electrolyte of mixed solvent containing dimethyl sulfoxide and preparation method thereof |
| CN108110321A (en) * | 2017-12-27 | 2018-06-01 | 河南省法恩莱特新能源科技有限公司 | A kind of lithium battery high-voltage electrolyte |
| CN109273763A (en) * | 2018-09-06 | 2019-01-25 | 贵州兴锂新能源科技有限公司 | It is a kind of using lithium titanate as the lithium-ion battery electrolytes of cathode |
| CN110943253A (en) * | 2019-10-24 | 2020-03-31 | 松山湖材料实验室 | High-voltage lithium ion battery combined electrolyte additive, electrolyte and battery thereof |
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