CN106887641A - A kind of ternary battery Overcharge prevention electrolyte and preparation method thereof - Google Patents
A kind of ternary battery Overcharge prevention electrolyte and preparation method thereof Download PDFInfo
- Publication number
- CN106887641A CN106887641A CN201710015032.2A CN201710015032A CN106887641A CN 106887641 A CN106887641 A CN 106887641A CN 201710015032 A CN201710015032 A CN 201710015032A CN 106887641 A CN106887641 A CN 106887641A
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- Prior art keywords
- organic solvent
- lithium
- battery
- carbonate
- overcharge
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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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
-
- 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
-
- 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
Abstract
The present invention proposes a kind of ternary battery Overcharge prevention electrolyte, consists of the following composition：Organic solvent, lithium salts, anti-overcharge additive, the mass ratio that the anti-overcharge additive accounts for organic solvent are 3~8%, and the anti-overcharge additive is biphenyl and/or cyclohexylbenzene, and the organic solvent is ethers and based organic solvent.The present invention also proposes the preparation method of the Overcharge prevention electrolyte.Overcharge prevention electrolyte proposed by the invention, by the immixture of BP and CHB, electropolymerization can be overcharged in over-charging of battery, block being filled with for electric current, be prevented effectively from that ternary dynamic lithium battery brings when overcharging catches fire or explosion phenomenon, so as to solve the problems, such as to perplex the overcharge safety of the ternary battery of industry all the time.
Description
Technical field
The invention belongs to battery material field, and in particular to a kind of ternary battery material, and preparation method thereof.
Background technology
Lithium battery is made up of positive pole, negative pole, barrier film, the big material of electrolyte four, and the electrolyte of lithium ion battery is generally liquid,
That is electrolyte.Electrolyte plays a part of to conduct electronics between battery plus-negative plate, and the quality of electrolyte property will be directly affected
The combination property of lithium ion battery.Because lithium ion battery charge and discharge potential is high, and positive pole is embedded with the larger lithium of chemism, because
This excellent electrolyte should meet claimed below：Chemical stability is good, ionic conductivity is high, temperature range is wide, safety non-toxic etc..
Ternary battery has high-energy-density, high working voltage, long service life, memory-less effect, course continuation mileage because of it
Long the advantages of, in recent years as focus of concern, in electrokinetic cell field, the positive surging emergence of ternary battery.But safety is asked
Topic governs the fast development of ternary battery always, especially solves to overcharge, the potential safety hazard such as acupuncture has turned into industry research
Emphasis.
Organic solvent is the main part of electrolyte, and the solvent commonly used in electrolyte of lithium-ion secondary battery has ethylene carbonate
Ester (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) etc..
Additive in electrolyte, according to its effect, mainly there is following a few classes：
(1) performance of SEI films is improved：Methyl phenyl ethers anisole or its halo derivatives are added in lithium-ion battery electrolytes, can
Improve the cycle performance of battery, reduce the irreversible capacity loss of battery.
(2) minor amount of water and the HF acid in electrolyte are reduced, such as carbodiimides can prevent LiPF6 from being hydrolyzed into
Acid, in addition, some metal oxides such as Al2O3, MgO, BaO, Li2CO3, CaCO3 etc. be used to remove HF it is clean.
(3) overcharge, overdischarge are prevented：Electrokinetic cell is very urgent to the requirement that battery overcharging resisting puts performance.Tradition is anti-
The measure of overcharge is to set protection circuit in inside battery, is now desired to adding additive in electrolyte, such additive
It is in conceptual phase.
The content of the invention
(1) technical problem to be solved
The technical problem to be solved in the present invention is, in view of the shortcomings of the prior art, there is provided a kind of Overcharge prevention electrolyte, effectively
Avoid what ternary dynamic lithium battery brought when overcharging from catching fire or explosion phenomenon, so as to solve to perplex industry all the time
The overcharge safety problem of ternary battery.
Manufacture method it is another object of the present invention to propose the Overcharge prevention electrolyte.
Third object of the present invention is to propose the ternary battery containing the Overcharge prevention electrolyte.
(2) technical scheme
The technical scheme for realizing above-mentioned purpose of the present invention is：
A kind of ternary battery Overcharge prevention electrolyte, consists of the following composition：Organic solvent, lithium salts, anti-overcharge additive,
The mass ratio that the anti-overcharge additive accounts for organic solvent is 3~8%, and the anti-overcharge additive is biphenyl (BP) and/or benzene
Butylcyclohexane (CHB), the organic solvent is ethers and based organic solvent；
The ether organic solvent is ether, ethyl methyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diformazan
One or more in ether, tetraethyleneglycol dimethyl ether, ethylene glycol monoemethyl ether, dioxolane, dioxane；The esters are organic molten
Agent is propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate, carbonic acid first butyl ester, ethylene
Butyl ester, dibutyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, chloro-ethylene carbonate, ethyl acetate, acetic acid
One or more in propyl ester, ethyl propionate, methyl butyrate.
Preferably, the anti-overcharge additive is biphenyl (BP) and cyclohexylbenzene (CHB), and the mass ratio of the two is 2：
2~4.
It is highly preferred that the organic solvent be 1 parts by volume ethers and 5~15 parts by volume based organic solvents mixing it is molten
Agent, the based organic solvent be propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate,
Two kinds in carbonic acid first butyl ester, the volume ratio of the two is 1：0.8~1.2.
Using the SEI films (solid electrolyte interface film) that stabilization can be set up in EC or EC+DMC composite electrolytes.Generally
Think, EC is the excellent electrolyte of lithium ion battery with a kind of mixed solvent of linear carbonate.Wherein ether organic solvent can
The electrical conductivity of electrolyte is improved as the cosolvent or additive of carbonic ester.
The present invention also proposes the method for preparing the ternary battery Overcharge prevention electrolyte, comprises the following steps：Stirring shape
To lithium salts is added in the organic solvent for constituting electrolyte under state, anti-overcharge additive is subsequently adding, preparation process control is organic molten
Agent temperature is 0~10 DEG C.
Wherein, before adding lithium salts in the organic solvent, the moisture of organic solvent is down to below 10ppm.Dry
Mode is the conventional method in this area, for example, process more than 12h using drier (molecular sieve or silica gel), is surveyed with moisture tester
Examination solvent water content.
Wherein, the organic solvent is prepared by the following method：- 45 DEG C are less than in dew point, oxygen content is less than 3ppm environment
Under, ethers and based organic solvent are prepared by volume proportion.
Wherein, the lithium salts is lithium iodide, lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium hexafluoro phosphate, trifluoro
One or more in pyrovinic acid lithium, lithium salts concentration in organic solvent is 0.8~1.5mol/L.
Wherein, the water content of the anti-overcharge additive is less than 2ppm.
Lithium ion battery containing ternary battery Overcharge prevention electrolyte of the present invention.
Described lithium ion battery, the positive electrode active materials of battery are nickel-cobalt-manganese ternary material or nickel cobalt aluminium ternary material,
The negative active core-shell material of battery is one or more in graphite, lithium titanate, Graphene, CNT；The diaphragm material of battery
For one or two in polypropylene, ceramics, polyethylene.
(3) beneficial effect
The beneficial effects of the present invention are：
Overcharge prevention electrolyte proposed by the invention, by the immixture of BP and CHB, can occur in over-charging of battery
Charge polymerization, blocking electric current is filled with, be prevented effectively from that ternary dynamic lithium battery brings when overcharging catch fire or explode shows
As so as to solve the problems, such as to perplex the overcharge safety of the ternary battery of industry all the time.
Specific embodiment
The present invention is now illustrated with following examples, but is not limited to the scope of the present invention.The hand used in embodiment
Section, unless otherwise instructed, uses the means that this area is conventional.
Material in embodiment, unless otherwise indicated, is purchased in market.
Embodiment 1
- 45 DEG C are less than in dew point, oxygen content is less than preparation ethylene carbonate, dimethyl carbonate, ethyl methyl ether under 3ppm environment
Organic solvent, by molecular sieve drying, its volume ratio is 5 to adding ingredient:5:1；When moisture is down to below 10ppm, while stirring
Mix side and add lithium hexafluoro phosphate, make the concentration of lithium hexafluoro phosphate for 1mol/L, be subsequently adding water content below 5ppm 2wt%'s
The CHB (in terms of the quality of organic solvent) of BP and 3wt%, adition process controls organic solvent temperature at 0-10 DEG C.Obtain hexafluoro
Lithium phosphate organic electrolyte.
Embodiment 2
- 45 DEG C are less than in dew point, oxygen content is less than preparation ethylene carbonate, dimethyl carbonate, ethyl methyl ether under 3ppm environment
Organic solvent, its volume ratio is 5:5:1；When moisture is down to below 10ppm, lithium hexafluoro phosphate is added while stirring, prepare molten
Hexafluorophosphoric acid lithium concentration is 1mol/L in liquid.BP of the water content in below 5ppm 5wt% is subsequently adding, adition process control is organic
Solvent temperature is at 0-10 DEG C.Obtain lithium hexafluoro phosphate organic electrolyte.
Embodiment 3
- 45 DEG C are less than in dew point, oxygen content is less than preparation ethylene carbonate, dimethyl carbonate, ethyl methyl ether under 3ppm environment
Organic solvent, its volume ratio is 5:5:1；When the near 10ppm of moisture and it is following when, lithium hexafluoro phosphate is added while stirring, then
Add water content in the CHB of below 5ppm 5wt%, adition process controls organic solvent temperature at 0-10 DEG C.Prepare six in solution
Lithium fluophosphate concentration is the organic electrolyte of 1mol/L.
Embodiment 4
A kind of lithium ion battery of the electrolyte comprising embodiment 1-3, the power lithium-ion battery includes：Housing, positive pole,
Negative pole, barrier film and electrolyte, positive pole use nickel-cobalt-manganese ternary pole piece, and negative pole is graphite, and barrier film is polypropylene (PP), and electrolyte is
The electrolyte provided in embodiment 1-3, the manufacturing process of lithium ion battery is：Both positive and negative polarity dispensing-both positive and negative polarity slurrying-both positive and negative polarity is applied
Cloth-both positive and negative polarity drying-both positive and negative polarity roll-in-both positive and negative polarity film-making-both positive and negative polarity winding-assembling-baking-slip casting-chemical conversion-sealing of hole-partial volume-
Product battery.
Battery is obtained with the ternary electrolyte using comparative example using ternary lithium ion battery provided in an embodiment of the present invention：
Comparative example 1, electrolyte is ethylene carbonate, dimethyl carbonate, ethyl methyl ether organic solvent, and its volume ratio is 5:5:1；Do not add wherein
Plus anti-overcharge additive；Comparative example 2, electrolyte is ethylene carbonate, dimethyl carbonate organic solvent, and its volume ratio is 5:5；Its
In without anti-overcharge additive, hexafluorophosphoric acid lithium concentration is 1mol/L in electrolyte.
Contrast test is carried out, negative pole selects Delanium, and battery core uses winding-structure, and capacity is 12Ah.Cycle charge-discharge
Multiplying power is 1C.The lithium ion battery that the present invention is provided is shown in Table 1 with the comparing result of current ternary lithium ion battery.
Overcharging experiment is：At 25 DEG C, a full electricity state cell is put into environmental chamber, stands 30min, it is ensured that monomer
Battery bulk temperature is consistent with temperature in environmental chamber；Overcharge is carried out to the cell, size of current is 1C, the time for overcharging
It is 90min；Record the outward appearance and temperature change of battery.
The embodiment lithium ion battery of table 1 and comparative example ternary lithium ion battery comparing result
| Tested number | Overcharge experiment | 25 DEG C of cycle lives |
| Embodiment 1 | Without catching fire, without blast | 500 residual capacities 92.8% |
| Embodiment 2 | Without catching fire, without blast | 500 residual capacities 91.5% |
| Embodiment 3 | Without catching fire, without blast | 500 residual capacities 90.6% |
| Comparative example 1 | Catch fire | 500 residual capacities 87.9% |
| Comparative example 2 | Catch fire | 500 residual capacities 87.3% |
Compare through overtesting, it was observed that the effect that BP and CHB are used in mixed way is better than individually addition one kind.Its mechanism may
It is that can overcharge electropolymerization rapidly in over-charging of battery after BP and CHB immixtures, so as to block electric current be filled with, effectively keeps away
That exempts from that ternary dynamic lithium battery brings when overcharging catches fire or explosion phenomenon, improves the security of ternary lithium battery.
The electrolyte prepared using BP and CHB additives as can be seen from Table 1, the cycle performance of lithium ion battery of its composition
Also very outstanding, residual capacity can keep 92.8% after 500 circulations, be much better than current ternary lithium ion battery.
Embodiment above is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is entered
Row is limited, and on the premise of design spirit of the present invention is not departed from, this area ordinary skill technical staff is to technical side of the invention
The all variations and modifications that case is made, all should fall into the protection domain of claims of the present invention determination.
Claims (10)
1. a kind of ternary battery Overcharge prevention electrolyte, it is characterised in that consist of the following composition：Organic solvent, lithium salts, anti-mistake
Fill additive, the mass ratio that the anti-overcharge additive accounts for organic solvent is 3~8%, the anti-overcharge additive be biphenyl and/
Or cyclohexylbenzene, the organic solvent is ethers and based organic solvent；
The ether organic solvent is ether, ethyl methyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, four
One or more in glycol dimethyl ether, ethylene glycol monoemethyl ether, dioxolane, dioxane；The based organic solvent is
Propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate, carbonic acid first butyl ester, ethyl butyl carbonate,
Dibutyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, chloro-ethylene carbonate, ethyl acetate, propyl acetate,
One or more in ethyl propionate, methyl butyrate.
2. ternary battery Overcharge prevention electrolyte according to claim 1, it is characterised in that the anti-overcharge additive is
Biphenyl and cyclohexylbenzene, the mass ratio of the two are 2：2~4.
3. ternary battery Overcharge prevention electrolyte according to claim 1, it is characterised in that the organic solvent is 1 body
The mixed solvent of product part ethers and 5~15 parts by volume based organic solvents, the based organic solvent is propene carbonate, carbonic acid
Two kinds in vinyl acetate, butylene, dimethyl carbonate, diethyl carbonate, carbonic acid first butyl ester, the volume ratio of the two is 1：
0.8~1.2.
4. the method for preparing ternary battery Overcharge prevention electrolyte described in any one of claims 1 to 3, it is characterised in that including
Following steps：To lithium salts is added in the organic solvent for constituting electrolyte under stirring, anti-overcharge additive is subsequently adding, prepared
Process control organic solvent temperature is 0~10 DEG C.
5. method according to claim 4, it is characterised in that before adding lithium salts in the organic solvent, will be organic
The moisture of solvent is down to below 10ppm.
6. method according to claim 4, it is characterised in that the organic solvent is prepared by the following method：In dew point
Less than -45 DEG C, oxygen content is prepared ethers and based organic solvent by volume proportion less than under 3ppm environment.
7. method according to claim 4, it is characterised in that the lithium salts is lithium iodide, lithium perchlorate, tetrafluoro boric acid
One or more in lithium, hexafluoroarsenate lithium, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, lithium salts concentration in organic solvent
It is 0.8~1.5mol/L.
8. the method according to any one of claim 4~7, it is characterised in that the water content of the anti-overcharge additive is small
In 2ppm.
9. the lithium ion battery of ternary battery Overcharge prevention electrolyte described in any one of claims 1 to 3 is contained.
10. lithium ion battery according to claim 9, it is characterised in that the positive electrode active materials of battery are nickel cobalt manganese three
First material or nickel cobalt aluminium ternary material, the negative active core-shell material of battery is in graphite, lithium titanate, Graphene, CNT
Plant or various；The diaphragm material of battery be polypropylene, ceramics, polyethylene in one or two.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710015032.2A CN106887641A (en) | 2017-01-09 | 2017-01-09 | A kind of ternary battery Overcharge prevention electrolyte and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710015032.2A CN106887641A (en) | 2017-01-09 | 2017-01-09 | A kind of ternary battery Overcharge prevention electrolyte and preparation method thereof |
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| CN106887641A true CN106887641A (en) | 2017-06-23 |
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| CN201710015032.2A Pending CN106887641A (en) | 2017-01-09 | 2017-01-09 | A kind of ternary battery Overcharge prevention electrolyte and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108682889A (en) * | 2018-04-28 | 2018-10-19 | 浙江天能能源科技股份有限公司 | A kind of lithium ion battery high-voltage electrolyte and its application |
| CN113540570A (en) * | 2021-09-16 | 2021-10-22 | 北京壹金新能源科技有限公司 | Electrolyte, preparation method and lithium ion battery comprising electrolyte |
| CN115312888A (en) * | 2022-06-21 | 2022-11-08 | 东莞市聚和新能源有限公司 | Overcharge-prevention high-rate battery and preparation method thereof |
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| JP2006324235A (en) * | 2005-04-20 | 2006-11-30 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| CN101777668A (en) * | 2010-02-05 | 2010-07-14 | 九江天赐高新材料有限公司 | Electrolyte for lithium manganese battery |
| CN104054207A (en) * | 2012-01-17 | 2014-09-17 | 丰田自动车株式会社 | Sealed lithium secondary battery |
| CN106252725A (en) * | 2016-08-31 | 2016-12-21 | 天津市捷威动力工业有限公司 | A kind of Overcharge prevention electrolyte based on ternary lithium ion battery and lithium ion battery |
-
2017
- 2017-01-09 CN CN201710015032.2A patent/CN106887641A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006324235A (en) * | 2005-04-20 | 2006-11-30 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| CN101777668A (en) * | 2010-02-05 | 2010-07-14 | 九江天赐高新材料有限公司 | Electrolyte for lithium manganese battery |
| CN104054207A (en) * | 2012-01-17 | 2014-09-17 | 丰田自动车株式会社 | Sealed lithium secondary battery |
| CN106252725A (en) * | 2016-08-31 | 2016-12-21 | 天津市捷威动力工业有限公司 | A kind of Overcharge prevention electrolyte based on ternary lithium ion battery and lithium ion battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108682889A (en) * | 2018-04-28 | 2018-10-19 | 浙江天能能源科技股份有限公司 | A kind of lithium ion battery high-voltage electrolyte and its application |
| CN113540570A (en) * | 2021-09-16 | 2021-10-22 | 北京壹金新能源科技有限公司 | Electrolyte, preparation method and lithium ion battery comprising electrolyte |
| CN115312888A (en) * | 2022-06-21 | 2022-11-08 | 东莞市聚和新能源有限公司 | Overcharge-prevention high-rate battery and preparation method thereof |
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