CN105186035A - Additive capable of improving high voltage performance of electrolyte and electrolyte containing additive - Google Patents
Additive capable of improving high voltage performance of electrolyte and electrolyte containing additive Download PDFInfo
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- CN105186035A CN105186035A CN201510470487.4A CN201510470487A CN105186035A CN 105186035 A CN105186035 A CN 105186035A CN 201510470487 A CN201510470487 A CN 201510470487A CN 105186035 A CN105186035 A CN 105186035A
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- electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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Abstract
The invention discloses an additive capable of improving high voltage performance of an electrolyte and the electrolyte containing the additive. The additive capable of improving the high voltage performance of the electrolyte, a lithium salt and other conventional additives are dissolved into a non-aqueous organic solvent to prepare a high-voltage electrolyte. The additive capable of improving the high voltage performance of the electrolyte disclosed by the invention is an organic phosphorus oxide compound, and can be oxidized and decomposed in preference to an electrolyte matrix solvent; and the decomposed product is deposited on the cathode surface to form a layer of protective layer which is similar to an anode SEI film, so that continuous oxidation and decomposition of the matrix solvent on the cathode surface are greatly stopped; and the high voltage performance of a lithium-ion battery is greatly improved.
Description
Technical field:
The present invention relates to a kind of can improve electrolyte high voltage capability additive and electrolyte containing this additive, belong to battery material technical field.
Background technology:
Lithium ion battery has been widely used in the fields such as portable electric appts, electric tool, energy storage device and electric automobile.But along with the continuous progress of technology and the sustainable development in market, the requirement of people to the flying power of lithium ion battery improves constantly, as improved the stand-by time of smart mobile phone, the course continuation mileage improving electric automobile etc.This makes the energy density promoting lithium ion battery become the key factor of above field progress.Improve the energy density of lithium ion battery, improving its operating voltage is basic choosing.
At present, the anode material for lithium-ion batteries of widespread commercial has the acid of LiFePO4, cobalt lithium, LiMn2O4, ternary material etc.Due to the restriction of positive electrode, the operating voltage of this type of lithium ion battery is generally no more than 4.4V, and the room for promotion of its energy density is very limited.Researcher have developed multiple high working voltage positive electrode, comprises rich lithium layered cathode material, spinel oxide LiNi0.5Mn1.504, olivine oxide LiCoP04 etc., their operating voltage all close to or reach 5V.But the carbonate group electrolyte of current main-stream is when charging voltage reaches 4.5V, carbonate solvent just can, in positive electrode surface oxidation Decomposition, make the performance of whole battery decline to a great extent.The matching problem of electrolyte seriously constrains applying of above-mentioned high-voltage anode material.Therefore, develop a kind of operating voltage that is applied to and become particularly urgent in the high-voltage lithium-ion battery electrolyte of more than 4.8V.
Summary of the invention:
The object of this invention is to provide a kind of can improve electrolyte high voltage capability additive and electrolyte containing this additive, can stop to a great extent base solvent the continued oxidation of positive electrode surface decompose and base solvent to the corrosion of positive pole battery core, the greatly high voltage capability of raising lithium ion battery.
For achieving the above object, the technical solution used in the present invention is:
The invention provides a kind of additive that can improve electrolyte high voltage capability, be organic oxidation phosphorus species, its structural formula can be expressed as:
Wherein, R1, R2, R3 are selected from one or more in alkyl, fluoroalkane alkyl, alkylene, fluoroolefin base, alkynes base, fluoroalkynes base, aryl and fluorinated aromatic hydrocarbon base.
Present invention also offers a kind of electrolyte containing the additive that can improve electrolyte high voltage capability, comprise non-aqueous organic solvent, high voltage additive, conventional additives, lithium salts.
The above-mentioned electrolyte containing the additive that can improve electrolyte high voltage capability, its preparation steps is as follows:
(1) mixed solvent is mixed to get after being dewatered by non-aqueous organic solvent;
(2) lithium salts is dissolved in the mixed solvent that step (1) obtains, lithium salt 0.8M-1.5M, obtains not containing the electrolyte of additive;
(3) additive that can improve electrolyte high voltage capability be dissolved in together with other conventional additives that step (2) obtains not containing in the electrolyte of additive, the quality improving the additive of electrolyte high voltage capability is the 0.1%-3% of solvent quality, the quality of other conventional additives is the 1%-10% of solvent quality, obtains Novel high voltage lithium-ion battery electrolytes.
Step (1) described non-aqueous organic solvent is at least two kinds in ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC).
Step (2) described lithium salts is the mixture of one or more of lithium hexafluoro phosphate (LiPF6), hexafluoroarsenate lithium (LiAsF6), lithium perchlorate (LiClO4), LiBF4 (LiBF4), dioxalic acid lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB) and bis trifluoromethyl sulfimide lithium (LiN (CF3SO2) 2), is preferably lithium hexafluoro phosphate (LiPF6).
Step (3) described conventional additives is at least one in vinylene carbonate (VC), 1,3-propane sultone (PS), fluorinated ethylene carbonate (FEC), adiponitrile (ADN).
The invention has the beneficial effects as follows: the described additive that can improve electrolyte high voltage capability; electrolyte matrices solvent oxidation can be had precedence over decompose; catabolite is deposited on positive electrode surface; form the protective layer of one deck similar negative pole SEI film; can stop to a great extent base solvent the continued oxidation of positive electrode surface decompose and base solvent to the corrosion of positive pole battery core, the greatly high voltage capability of raising lithium ion battery.Meanwhile, high-voltage electrolyte preparation process of the present invention is simple, and cost is lower, is convenient to large-scale commercial and produces.
Embodiment:
For illustrating this aspect further, describe the preferred embodiments of the invention below in conjunction with specific embodiment, these describe just in order to further illustrate advantage of the present invention, instead of limiting to the claimed invention.
Embodiment 1
Can improve an additive for electrolyte high voltage capability, its structural formula is as follows:
Structural formula (one)
Use the preparation method of electrolyte of above-mentioned additive, comprise following steps:
(1), after ethylene carbonate (EC) and methyl ethyl carbonate (EMC) being dewatered respectively, 3: 7 mixing, stir, obtain mixed solvent in mass ratio;
(2) lithium hexafluoro phosphate is dissolved in above-mentioned mixed solvent, its concentration is 1M/L, obtains not containing the electrolyte of additive;
(3) to not adding the additive shown in structural formula () containing in the electrolyte of additive, its quality is 3% of mixed solvent quality, add quality simultaneously and be respectively 1% of mixed solvent quality, the vinylene carbonate (VC) of 1% and 1,3-propane sultone (PS), stirring and dissolving obtains high-voltage electrolyte.
Embodiment 2
Can improve an additive for electrolyte high voltage capability, its structural formula is as follows:
Structural formula (two)
Use the preparation method of electrolyte of above-mentioned additive, comprise following steps:
(1), after ethylene carbonate (EC) and methyl ethyl carbonate (EMC) being dewatered respectively, 3: 7 mixing, stir, obtain mixed solvent in mass ratio;
(2) lithium hexafluoro phosphate is dissolved in above-mentioned mixed solvent, its concentration is 1M/L, obtains not containing the electrolyte of additive;
(3) to not adding the additive shown in structural formula (two) containing in the electrolyte of additive, its quality is 2.5% of mixed solvent quality, add quality simultaneously and be respectively 1% of mixed solvent quality, the vinylene carbonate (VC) of 1% and 1,3-propane sultone (PS), stirring and dissolving obtains high-voltage electrolyte.
Embodiment 3
Can improve an additive for electrolyte high voltage capability, its structural formula is as follows:
Structural formula (three)
Use the preparation method of electrolyte of above-mentioned additive, comprise following steps:
(1), after ethylene carbonate (EC) and methyl ethyl carbonate (EMC) being dewatered respectively, 3: 7 mixing, stir, obtain mixed solvent in mass ratio;
(2) lithium hexafluoro phosphate is dissolved in above-mentioned mixed solvent, its concentration is 1M/L, obtains not containing the electrolyte of additive;
(3) to not adding the additive shown in structural formula (three) containing in the electrolyte of additive, its quality is 1% of mixed solvent quality, add quality simultaneously and be respectively 1% of mixed solvent quality, the vinylene carbonate (VC) of 1% and 1,3-propane sultone (PS), stirring and dissolving obtains high-voltage electrolyte.
Comparative example 1:
Preparation does not contain the electrolyte of the additive that can improve electrolyte high voltage capability as a comparison, comprises following steps:
(1), after ethylene carbonate (EC) and methyl ethyl carbonate (EMC) being dewatered respectively, 3: 7 mixing, stir, obtain mixed solvent in mass ratio;
(2) lithium hexafluoro phosphate is dissolved in above-mentioned mixed solvent, its concentration is 1M/L, obtains not containing the electrolyte of additive;
(3) add vinylene carbonate (VC) and 1, the 3-propane sultone (PS) that quality is respectively 1%, 1% of mixed solvent quality, stirring and dissolving obtains final electrolyte.
Effect detects:
Take LiCoPO4 as positive electrode, be the LiCoPO4 of 94: 3: 3 by mass ratio, Kynoar (PVDF), conductive black size mixing in 1-methyl-9-pyrrolidinone solvent, gained slurry double-faced uniform is coated on aluminium foil, drying, roll extrusion, the anode pole piece after cutting.
Take graphite as negative material, be the butadiene-styrene rubber (SBR) of 4: 1: 95 by mass ratio, sodium carboxymethylcellulose (CMC), graphite sizes mixing in deionized water, gained slurry double-faced uniform is coated on Copper Foil, drying, roll extrusion, the cathode pole piece after cutting.
By above-mentioned both positive and negative polarity pole piece and the composite diaphragm that is made up of polypropylene, polyethylene, obtain square dry battery core by lamination, through high-temperature baking, filling the various embodiments described above and comparative example electrolyte, leave standstill, once change into, encapsulate and secondary change into after must experimental cell.
Carry out the performance test of room temperature 3.0V-5.0V cycle of higher pressure to above-mentioned experimental cell, charging and discharging currents is 0.1C, and circulate 50 weeks, test result sees attached list 1.
Table one embodiment and comparative example battery high voltage loop test result
| Experimental cell | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Capability retention | More than 80% | More than 80% | More than 80% | Less than 65% |
As can be seen from table one, embodiment 1,2, the battery capacity conservation rate of 3 comparatively comparative example is all improved largely, and illustrates that high voltage additive provided by the invention can significantly improve the high voltage capability of lithium ion battery, simultaneously, electrolyte preparation technology containing this additive is simple, is easy to apply.
Claims (6)
1. can improve an additive for electrolyte high voltage capability, be organic oxidation phosphorus species, it is characterized in that: its structural formula can be expressed as:
Wherein, R1, R2, R3 are selected from one or more in alkyl, fluoroalkane alkyl, alkylene, fluoroolefin base, alkynes base, fluoroalkynes base, aryl and fluorinated aromatic hydrocarbon base.
2. contain an electrolyte for the additive that can improve electrolyte high voltage capability, it is characterized in that: comprise non-aqueous organic solvent, the additive that can improve electrolyte high voltage capability, conventional additives, lithium salts.
3. the electrolyte containing the additive that can improve electrolyte high voltage capability according to claim 2, is characterized in that: its preparation steps is as follows:
(1) mixed solvent is mixed to get after being dewatered by non-aqueous organic solvent;
(2) lithium salts is dissolved in the mixed solvent that step (1) obtains, lithium salt 0.8M-1.5M, obtains not containing the electrolyte of additive;
(3) additive that can improve electrolyte high voltage capability be dissolved in together with other conventional additives that step (2) obtains not containing in the electrolyte of additive, the quality improving the additive of electrolyte high voltage capability is the 0.1%-3% of solvent quality, the quality of other conventional additives is the 1%-10% of solvent quality, obtains Novel high voltage lithium-ion battery electrolytes.
4. the electrolyte containing the additive that can improve electrolyte high voltage capability according to Claims 2 or 3, is characterized in that: described non-aqueous organic solvent is at least two kinds in ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC).
5. the electrolyte containing the additive that can improve electrolyte high voltage capability according to Claims 2 or 3, it is characterized in that: described lithium salts is the mixture of one or more of lithium hexafluoro phosphate (LiPF6), hexafluoroarsenate lithium (LiAsF6), lithium perchlorate (LiClO4), LiBF4 (LiBF4), dioxalic acid lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiDFOB) and bis trifluoromethyl sulfimide lithium (LiN (CF3SO2) 2), be preferably lithium hexafluoro phosphate (LiPF6).
6. the electrolyte containing the additive that can improve electrolyte high voltage capability according to Claims 2 or 3, it is characterized in that: the described quality improving the additive of electrolyte high voltage capability is the 0.1%-3% of solvent quality, the quality of other conventional additives is the 1%-10% of solvent quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510470487.4A CN105186035A (en) | 2015-07-30 | 2015-07-30 | Additive capable of improving high voltage performance of electrolyte and electrolyte containing additive |
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| CN201510470487.4A CN105186035A (en) | 2015-07-30 | 2015-07-30 | Additive capable of improving high voltage performance of electrolyte and electrolyte containing additive |
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| CN201510470487.4A Pending CN105186035A (en) | 2015-07-30 | 2015-07-30 | Additive capable of improving high voltage performance of electrolyte and electrolyte containing additive |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105406124A (en) * | 2015-12-31 | 2016-03-16 | 哈尔滨工业大学 | Electrolyte for improving high temperature and high voltage performance of lithium ion battery and application thereof in lithium ion battery |
| CN109065951A (en) * | 2018-07-31 | 2018-12-21 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN112928327A (en) * | 2019-12-06 | 2021-06-08 | 宁德国泰华荣新材料有限公司 | Secondary battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110151336A1 (en) * | 2009-12-22 | 2011-06-23 | Samsung Sdi Co., Ltd. | Lithium battery |
| CN102916223A (en) * | 2011-08-05 | 2013-02-06 | 索尼公司 | Nonaqueous electrolytic solution, nonaqueous electrolytic secondary battery, battery pack, electronic device |
| CN104218256A (en) * | 2013-05-29 | 2014-12-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Lithium ion battery high voltage electrolyte additive, electrolyte, preparation method of electrolyte, and lithium ion secondary battery |
-
2015
- 2015-07-30 CN CN201510470487.4A patent/CN105186035A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110151336A1 (en) * | 2009-12-22 | 2011-06-23 | Samsung Sdi Co., Ltd. | Lithium battery |
| CN102916223A (en) * | 2011-08-05 | 2013-02-06 | 索尼公司 | Nonaqueous electrolytic solution, nonaqueous electrolytic secondary battery, battery pack, electronic device |
| CN104218256A (en) * | 2013-05-29 | 2014-12-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Lithium ion battery high voltage electrolyte additive, electrolyte, preparation method of electrolyte, and lithium ion secondary battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105406124A (en) * | 2015-12-31 | 2016-03-16 | 哈尔滨工业大学 | Electrolyte for improving high temperature and high voltage performance of lithium ion battery and application thereof in lithium ion battery |
| CN105406124B (en) * | 2015-12-31 | 2019-03-19 | 哈尔滨工业大学 | A kind of electrolyte improving high-temperature lithium ion battery and high voltage capability and its application in lithium ion battery |
| CN109065951A (en) * | 2018-07-31 | 2018-12-21 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN112928327A (en) * | 2019-12-06 | 2021-06-08 | 宁德国泰华荣新材料有限公司 | Secondary battery |
| CN112928327B (en) * | 2019-12-06 | 2024-12-20 | 宁德国泰华荣新材料有限公司 | A secondary battery |
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Application publication date: 20151223 |