CN104037453B - Functional electrolyte for preventing overcharge of lithium battery and production method of functional electrolyte - Google Patents
Functional electrolyte for preventing overcharge of lithium battery and production method of functional electrolyte Download PDFInfo
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- CN104037453B CN104037453B CN201410275652.6A CN201410275652A CN104037453B CN 104037453 B CN104037453 B CN 104037453B CN 201410275652 A CN201410275652 A CN 201410275652A CN 104037453 B CN104037453 B CN 104037453B
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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
- H01M10/056—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
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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
- H01M10/058—Construction or manufacture
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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 provides functional electrolyte for preventing the overcharge of a lithium battery and a production method of the functional electrolyte. The functional electrolyte comprises basic electrolyte and a functional additive, wherein the basic electrolyte comprises a carbonic ester type mixed solvent, lithium hexafluorophosphate and vinylene carbonate; the carbonic ester type mixed solvent comprises ethylene carbonate, ethyl methyl carbonate and propylene carbonate; the functional additive comprises 2, 3, 4-trifluorobiphenyl and 1, 3-propene sulfonic acid lactone. The production method comprises the following steps: adding the ethylene carbonate, the ethyl methyl carbonate and the propylene carbonate into a clean container in sequence; reducing the temperature to room temperature, and then adding the lithium hexafluorophosphate; standing for clarification, and then adding the vinylene carbonate, the 1, 3-propene sulfonic acid lactone and the 2, 3, 4-trifluorobiphenyl; and standing for clarification for spare use. The functional electrolyte provided by the invention has the advantages that the occurrence of the safety problems such as ignition and explosion caused by the overcharge of the lithium battery can be effectively prevented, so that the safety of the battery is improved, the high-temperature circulating performance of the lithium battery is improved, and the functional electrolyte is strong in applicability and can be used in multiple electro-chemical systems.
Description
Technical field
The present invention relates to lithium battery electrolytes technical field, particularly relates to a kind of feature electrolyte of preventing over charging of lithium cell
And its production method.
Background technology
Lithium battery refers to the battery containing lithium in electrochemical system, and chargeable lithium metal battery is born from the nineties in last century
Since, due to its superior security, specific capacity, self-discharge rate and cost performance, notebook computer, hand are widely used in
The miniaturized electronics such as machine, digital camera, Mp 3 player and medicine equipment, as driving power supply.
Lithium battery includes positive pole, negative pole, electrolyte and barrier film, and lithium ion occurs oxidation on positive pole and negative pole and reduces anti-
Should cause electronics embedded with abjection and then produce electric energy.If lithium cell charging is incorrect when causing to overcharge, the electricity of electrode
Position is higher, easily causes solvolysis reaction, and reaction raises the temperature of battery, causes battery explosion, on fire, causes to estimate
The consequence of amount, and flexible-packed battery is susceptible to inflatable in storage, affects battery performance.
For the shortcoming of electrolyte itself, researcher adds a small amount of " chemical substance " to form function in electrolyte system
Electrolyte, in inside battery a kind of anti-overcharge electrochemistry self-protective mechanism, this kind of " changing with some special efficacies are set up
Learn material " it is referred to as " additive " or " functional molecular ".As D.Aurbach et al. (Electrochim.Acta2002) has found,
Vinylene carbonate (VC) can be reduced prior to solvation lithium ion, and in electrode surface excellent SEI films are formed.United States Patent (USP)
US5776627 discloses a kind of anti-overcharge additive biphenyl, and when over-charging of battery, aerogenesis additive biphenyl will be aggregated in electrode
Surface forms SEI films, prevents the migration of lithium ion, improves the internal resistance of cell so as to the security performance of power-off and then raising battery.
SEI films have electronic isolation, insoluble in electrolyte in, with certain mechanical strength, toughness, can reduce graphite can not
Excellent embedding, the de- lithium cycle performance of inverse capacity and holding.But, the film, than relatively low, can cause battery to the conductivity of lithium ion
Performance in proper order and storage life significantly reduce.Therefore, a kind of suitable overcharge protection additives are found, SEI films is kept away
Exempt to overcharge the safety problem for causing, be unlikely to affect battery charging and discharging performance again, be the technical problem for being badly in need of solving at present.
The content of the invention
The present invention proposes a kind of feature electrolyte and its production method of preventing over charging of lithium cell, for solving background technology
In the problems referred to above.
The technical scheme is that what is be achieved in that：
A kind of feature electrolyte of preventing over charging of lithium cell, including basic electrolyte and functional additive, basis electrolysis
Liquid includes carbonates mixed solvent, lithium hexafluoro phosphate and vinylene carbonate (VC), and carbonates mixed solvent includes carbonic acid
Vinyl acetate (EC), methyl ethyl carbonate (DME) and propene carbonate (PC)；Functional additive includes 2,3,4- trifluoro-biphenyls.
As described in the background art, when battery is overcharged, the feature electrolyte of the preventing over charging of lithium cell of the present invention
Generation voltolisation is reacted：Polymeric membrane (or passivating film SEI) is generated in electrode surface, the internal resistance of cell is increased rapidly, prevent battery from entering
One step is overcharged, so as to effectively prevent battery explosion.But, the film, than relatively low, can cause to the conductivity of lithium ion
The charge-discharge performance of battery is significantly reduced.In order to overcome this defect, the present invention to the addition of the trifluoro of functional additive 2,3,4-
Biphenyl, its HOMO track can be far above other solvents in electrolyte, and its oxidation potential is less than all of solvent, therefore in battery
When overcharging there is oxidation Decomposition in 2,3,4- trifluoro-biphenyls prior to electrolyte solvent, in the similar negative terminal surface of anode Surface Creation
SEI films, separate contact of the electrolyte with electrode surface, compared with existing anti-overcharge additive biphenyl, cyclohexyl benzene, add
After 2,3,4- trifluoro-biphenyls, SEI film forming thickness is thinner, therefore can effectively prevent battery explosion, will not make again in battery
Resistance increases, and is unlikely to have undesirable effect the charge-discharge performance of battery, and lithium battery can be made to have good storage performance.
Preferably, functional additive also includes 1,3- propene sultones (PST).
The addition of 1,3- propene sultone (PST), can be effectively improved the cycle performance of lithium battery, can especially improve lithium electricity
The high temperature cyclic performance in pond so that lithium battery meets 300 charge and discharges more than 85% and requires.
Preferably, the percent by volume of each component is in carbonates mixed solvent：Ethylene carbonate 25～45%, carbon
Sour methyl ethyl ester is 45～75%, and propene carbonate is 5～10%.
Preferably, substance withdrawl syndrome of the lithium hexafluoro phosphate in carbonates mixed solvent is 1.5mol/L, and carbonic acid is sub-
Percentage by weight of the vinyl acetate in the total mixture of carbonates mixed solvent and lithium hexafluoro phosphate is 1%.
Preferably, 1,3- propene sultones are not more than 5% with the percentage by weight of basic electrolyte, 2,3,4- trifluoros connection
Benzene is not more than 5% with the percentage by weight of basic electrolyte.
Preferably, functional additive 1,3- propene sultones and 2,3,4- trifluoro-biphenyls meet following requirement：Purity
>=99.9%, moisture≤20ppm, alkaline insoluble matter≤5ppm, heavy metal≤1ppm, chloride≤1ppm, sulfate≤5ppm,
Color≤20APHA.
Basic electrolyte meets following requirement：Purity >=99.9% (GC), moisture≤20ppm, alkalescence insoluble matter≤5ppm,
Heavy metal≤1ppm.Chloride≤1ppm, sulfate≤5ppm, color≤20APHA；Lithium hexafluoro phosphate meets following requirement：It is pure
Degree >=99.9%, moisture≤10ppm, free acid in terms of HF≤50ppm, other particles Na, K, Fe, Ni etc.≤2ppm.
The invention allows for a kind of production method of the feature electrolyte of preventing over charging of lithium cell, including following step is prepared
Suddenly：
The first step, sequentially adds methyl ethyl carbonate, ethylene carbonate (being molten into liquid in advance), propene carbonate to totally
In container；
Second step, after the mixed solution temperature in the first step is down to room temperature, adds lithium hexafluoro phosphate；
3rd step, the mixed solution obtained by second step is placed and add after clarification vinylene carbonate, 1,3- propene sulfonic acids
Lactone and 2,3,4- trifluoro-biphenyls；
4th step, it is stand-by after the mixed solution obtained by the 3rd step is placed for a period of time.
Above-mentioned preparation is carried out under strict control raw material and environment, and the relative humidity of atmospheric environment is less than 1%, dew point temperature
- 50 DEG C of degree.In 3rd step, vinylene carbonate, 1,3- propene sultones and 2, the addition of 3,4- trifluoro-biphenyls is without order
Limit.
Preferably, in the 3rd step, place and add again in vinylene carbonate, 1,3- propene sulfonic acids after at least 3h after clarification
Ester and 2,3,4- trifluoro-biphenyls.
Preferably, in the 4th step, placing at least 6h can use after its solution is uniform.
Compared with prior art, beneficial effects of the present invention are：
1st, can effectively prevent lithium battery overcharge cause it is on fire, blast etc. safety problem generation, increased the peace of battery
Quan Xing；
2nd, charge and discharge efficiency high, good cycle, can meet 300 charge and discharge requirements more than 85%, can especially improve lithium electricity
The high temperature cyclic performance in pond；
3rd, the storge quality of battery can be increased, other performances of lithium battery are not affected；
4th, strong applicability, can be used for various electrochemical systems such as 18650 cylindrical batteries, 042025 flexible-packed battery,
043048 rectangular cell etc..
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
Embodiment 1
45ml EC, 45ml DME, 10ml PC are added in clean container successively；After being down to room temperature, to above-mentioned mixing
22.79g LiBF are added in thing6Its substance withdrawl syndrome is set to be 1.5mol/L；After placing clarification, after 3 hours 13.92g is added
VC (is EC, DME, PC and LiBF6Total percentage by weight is for 1%)；After placing 6h.
Embodiment 2
After embodiment 1 adds 13.92g VC, 7.66g2,3, the 4- trifluoro-biphenyls (weight with basic electrolyte are added
Percentage is that 5%), remaining is same as Example 1.
Embodiment 3
After embodiment 1 adds 13.92g VC, add 7.66g PST (is with the percentage by weight of basic electrolyte
5%), remaining is same as Example 1.
Embodiment 4
After embodiment 1 adds 13.92g VC, add 4.59g PST (is with the percentage by weight of basic electrolyte
3%) and 1.53g2,3,4- trifluoro-biphenyls (being 1% with the percentage by weight of basic electrolyte), remaining is same as Example 1.
Embodiment 5
After embodiment 1 adds 13.92g VC, add 4.59g PST (is with the percentage by weight of basic electrolyte
3%) and 3.06g2,3,4- trifluoro-biphenyls (being 2% with the percentage by weight of basic electrolyte), remaining is same as Example 1.
Embodiment 6
After embodiment 1 adds 13.92g VC, add 4.59g PST (is with the percentage by weight of basic electrolyte
3%) and 6.12g2,3,4- trifluoro-biphenyls (being 4% with the percentage by weight of basic electrolyte), remaining is same as Example 1.
Embodiment 7
After embodiment 1 adds 13.92g VC, add 1.53g PST (is with the percentage by weight of basic electrolyte
1%) and 4.59g2,3,4- trifluoro-biphenyls (being 3% with the percentage by weight of basic electrolyte), remaining is same as Example 1.
Embodiment 8
Mixed solvent in embodiment 7 is replaced with：25ml EC、75ml DME、5ml PC.Remaining is same as Example 7.
Embodiment 9
Mixed solvent in embodiment 7 is replaced with：35ml EC、57ml DME、8ml PC.Remaining is same as Example 7.
By the electrolyte in above-mentioned 9 embodiments be filled into respectively design capacity be 920mAh 413952 batteries with 2C times
Rate is crossed and is charged to 5V, and the test such as acupuncture, short circuit, thermal shock, heavy impact has been carried out afterwards, and test result is as described in table one.
Can be seen that from table one, the feature electrolyte of preventing over charging of lithium cell prepared by the present invention is greatly improved battery
Security performance.
In addition, being also circulated 300 weeks, 2C multiplying power dischargings test in 1 month, test result such as table two being shelved under 65 DEG C of high temperature
It is shown.As can be seen from Table II, the feature electrolyte of preventing over charging of lithium cell prepared by the present invention is for improving lithium battery
Cycle performance greatly improves, and can especially improve the high temperature cyclic performance of lithium battery so that lithium battery can meet 300 times more than 85%
Charge and discharge require.
Table one
Table two
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (6)
1. the feature electrolyte of a kind of preventing over charging of lithium cell, it is characterised in that：Including basic electrolyte and functional additive,
The basic electrolyte includes carbonates mixed solvent, lithium hexafluoro phosphate and vinylene carbonate, the carbonates mixing
Solvent includes ethylene carbonate, methyl ethyl carbonate and propene carbonate；
The functional additive includes 2,3,4- trifluoro-biphenyls；
The functional additive also includes 1,3- propene sultones；
The percent by volume of ethylene carbonate, methyl ethyl carbonate and propene carbonate is in the carbonates mixed solvent：Carbon
Vinyl acetate 25～45%, methyl ethyl carbonate is 45～75%, and propene carbonate is 5～10%.
2. the feature electrolyte of preventing over charging of lithium cell according to claim 1, it is characterised in that：In 1,3- propene sulfonic acids
Ester and the basic electrolyte phase weight/power ratio ratio no more than 5%, 2,3,4- trifluoro-biphenyls and the basic electrolyte phase weight/power ratio
Than being not more than 5%.
3. the feature electrolyte of preventing over charging of lithium cell according to claim 1, it is characterised in that：The feature addition
Agent 1,3- propene sultones and 2,3,4- trifluoro-biphenyls meet following requirement：Purity >=99.9%, moisture≤20ppm, alkalescence
Insoluble matter≤5ppm, heavy metal≤1ppm, chloride≤1ppm, sulfate≤5ppm, color≤20APHA.
4. a kind of production method of the feature electrolyte of the preventing over charging of lithium cell as described in any one of claim 2-3, it is special
Levy and be：Including following preparation steps：
The first step, sequentially adds methyl ethyl carbonate, melts ethylene carbonate, propene carbonate for liquid in advance to clean container
In；
Second step, after the mixed solution temperature in the first step is down to room temperature, adds lithium hexafluoro phosphate；
3rd step, the mixed solution obtained by second step is placed and add after clarification vinylene carbonate, 1,3- propene sultones
With 2,3,4- trifluoro-biphenyls；
4th step, it is stand-by after the mixed solution obtained by the 3rd step is placed for a period of time.
5. the production method of the feature electrolyte of preventing over charging of lithium cell according to claim 4, it is characterised in that：It is described
In 3rd step, to place and add vinylene carbonate, 1,3- propene sultones and 2,3,4- trifluoros again after at least 3h after clarification
Biphenyl.
6. the production method of the feature electrolyte of preventing over charging of lithium cell according to claim 4, it is characterised in that：It is described
At least 6h is placed in 4th step can be used after its solution is uniform.
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| CN104037453B true CN104037453B (en) | 2017-04-12 |
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| CN105047992B (en) * | 2015-07-21 | 2018-05-08 | 宁德新能源科技有限公司 | Electrolyte and the lithium ion battery including the electrolyte |
| CN106505245A (en) * | 2016-12-27 | 2017-03-15 | 石家庄圣泰化工有限公司 | A kind of triketone electrolyte for silicium cathode lithium battery |
| WO2021115316A1 (en) * | 2019-12-10 | 2021-06-17 | 中化蓝天集团有限公司 | Process and system for producing lipf6, and mixture crystal, composition, electrolyte solution and lithium battery containing lipf6 |
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| US20080193852A1 (en) * | 2006-02-03 | 2008-08-14 | Sanyo Electric Co., Ltd. | Nonaqueous Electrolyte Secondary Battery |
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Address after: 051430 douyu Industrial Zone, Luancheng County, Shijiazhuang City, Hebei Province Patentee after: Hebei Shengtai Materials Co., Ltd. Address before: 051430 douyu Industrial Zone, Luancheng County, Shijiazhuang City, Hebei Province Patentee before: SHIJIAZHUANG SHENGTAI CHEMICAL Co.,Ltd. |
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