CN105914402B - A kind of nonaqueous electrolytic solution and lithium ion battery - Google Patents
A kind of nonaqueous electrolytic solution and lithium ion battery Download PDFInfo
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- CN105914402B CN105914402B CN201610515308.9A CN201610515308A CN105914402B CN 105914402 B CN105914402 B CN 105914402B CN 201610515308 A CN201610515308 A CN 201610515308A CN 105914402 B CN105914402 B CN 105914402B
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- electrolytic solution
- nonaqueous electrolytic
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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
Abstract
This application involves a kind of nonaqueous electrolytic solution, including organic solvent, electrolytic salt and additive, contain barbital acid compounds in the additive；By the way that the cycle performance of battery can be significantly improved using barbital acid compounds as functional additive.
Description
Technical field
This application involves technical field of lithium batteries, and in particular to a kind of nonaqueous electrolytic solution and lithium ion battery.
Background technique
Lithium ion battery is because having many advantages, such as that specific energy is high, having extended cycle life, self discharge is small, is widely used in consumer
In electronic product and energy storage and power battery.With the extensive use of lithium ion battery, use environment also tends to be more already
Kind multiplicity, it is higher and higher to the life requirements of battery.For example, battery is in the case where big multiplying power fast charging and discharging still with longer
Service life, work long hours still in high temperature without security risk etc..
The service life of lithium ion battery is influenced by factors, wherein weight of the nonaqueous electrolytic solution as lithium ion battery
Component part is wanted, there is great influence to it.The dynamic performance of battery can be improved by nonaqueous electrolytic solution, reduce big times
Rate polarizes, and positive and negative anodes interface stability is during circulation and high temperature storage to achieve the purpose that improve service life, safety.
Summary of the invention
The first purpose of the application is to provide a kind of nonaqueous electrolytic solution.
The second purpose of parent itself is to provide a kind of lithium ion battery.
The application's the specific technical proposal is:
This application involves a kind of nonaqueous electrolytic solution, including organic solvent, electrolytic salt and additive, contain in the additive
There are barbital acid compounds.
Preferably, it is at least one of formula (I) compound represented that the barbital acid compounds, which are selected from structural formula,
Wherein,
R11、R12It is each independently selected from substituted or unsubstituted C1~12Alkyl, substituted or unsubstituted C1~12Alkenyl takes
Generation or unsubstituted C6~26Aryl；
R13、R14It is each independently selected from hydrogen, amino, substituted or unsubstituted C1~12Alkyl, substituted or unsubstituted C1~12
Alkenyl, substituted or unsubstituted C6~26Aryl ,-NH-R ', wherein R ' is substituted or unsubstituted C1~12Alkyl amine group；
X is selected from O and S；
Substituent group is selected from halogen.
Preferably, wherein
R11、R12It is each independently selected from substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl；
R13、R14It is each independently selected from hydrogen, substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl, amino.
Preferably, the barbital acid compounds are selected from least one of following compound,
Preferably, mass percentage of the barbital acid compounds in the nonaqueous electrolytic solution be 0.01%~
3%.
Preferably, mass percentage of the barbital acid compounds in the nonaqueous electrolytic solution be 0.05%~
2%.
Preferably, the organic solvent includes at least one of cyclic carbonate, linear carbonate and carboxylate
Preferably,
The cyclic carbonate is in ethylene carbonate, propene carbonate, gamma-butyrolacton, fluorinated ethylene carbonate
It is at least one；
The linear carbonate is selected from dimethyl carbonate, butylene, diethyl carbonate, dipropyl carbonate, carbonic acid first
At least one of ethyl ester, methyl propyl carbonate, ethyl propyl carbonic acid ester；
The carboxylate be selected from methyl formate, Ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate,
At least one of methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate.
Preferably, at least one in nitrogen, element sulphur, fluorine element, boron element, P elements is contained in the electrolytic salt
Kind；Preferably, the electrolytic salt is selected from lithium hexafluoro phosphate LiPF6, double trifluoromethanesulfonimide lithium LiN (CF3SO2)2, it is double
(fluorine sulphonyl) imine lithium Li (N (SO2F)2), di-oxalate lithium borate LiB (C2O4)2, difluorine oxalic acid boracic acid lithium LiBF2(C2O4) in
It is at least one.
This application involves a kind of lithium ion battery, including positive plate, negative electrode tab, be arranged at intervals at positive plate and negative electrode tab it
Between isolation film and electrolyte, the electrolyte is preceding any nonaqueous electrolytic solution.
Technical solution provided by the present application can achieve it is following the utility model has the advantages that
Compared with prior art, the application is by can significantly change using barbital acid compounds as functional additive
Kind cycle performance of battery.
Specific embodiment
To keep the purposes, technical schemes and advantages of the application clearer, below in conjunction with the embodiment of the present application, to this Shen
Technical solution please is clearly and completely described, it is clear that and described embodiment is some embodiments of the present application, without
It is whole embodiments.Based on technical solution provided by the present application and given embodiment, those skilled in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall in the protection scope of this application.
This application involves a kind of nonaqueous electrolytic solutions, including organic solvent, electrolytic salt and additive；Contain in the additive
There are barbital acid compounds.
Studies have shown that the oxidizing potential of barbital acid compounds is lower than solvent, can be aoxidized in battery core positive electrode surface poly-
It closes and forms fine and close SEI film (CEI), effectively reduce solvent in the decomposition of anode, very to the performance of battery
It is beneficial；This is because the polymer that barbital acid compounds and lithium are formed be covered on positive electrode surface relative to lithium alkylide be more difficult by
Solvent dissolution, CEI are more stable.It can effectively prevent positive electrode and nonaqueous electrolytic solution and side reaction occur in positive electrode surface, and
The increase of positive interface impedance in cyclic process can effectively be reduced.After barbital acid compounds polymerization film formation, it can prevent
Positive electrode as Mn, Co dissolution, prevent O from discharging, keep battery swollen to prevent O and nonaqueous electrolytic solution that oxidation production gas occurs
It is swollen.The product that barbital acid compounds are formed simultaneously contains O, and the group that it is good that N etc. leads ionic nature is covered on positive electrode surface will not
The conduction of lithium ion is impacted.Barbital acid compounds can improve battery core cyclicity as electrolysis additive well
Energy.
As a kind of improvement of the application nonaqueous electrolytic solution, it is formula that the application barbital acid compounds, which are selected from structural formula,
(1) at least one of compound represented,
Wherein,
R11、R12It is each independently selected from substituted or unsubstituted C1~12Alkyl, substituted or unsubstituted C1~12Alkenyl takes
Generation or unsubstituted C6~26Aryl；
R13、R14It is each independently selected from hydrogen, amino, substituted or unsubstituted C1~12Alkyl, substituted or unsubstituted C1~12
Alkenyl, substituted or unsubstituted C6~26Aryl ,-NH-R ', wherein R ' is substituted or unsubstituted C1~12Alkyl amine group；
X is selected from O and S；
Substituent group is selected from halogen, such as F, Cl.
As a kind of improvement of the application,
R11、R12It is each independently selected from substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted C1~6Alkenyl, substitution
Or unsubstituted phenyl；
R13、R14It is each independently selected from hydrogen, substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted C1~6Alkene
Base, substituted or unsubstituted phenyl, substituted or unsubstituted C1~6Aminoalkyl, amino, by C1~6Alkyl-substituted imido
Base.
As a kind of improvement of the application,
R11、R12It is each independently selected from substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl；
R13、R14It is each independently selected from hydrogen, substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl, amino.
As a kind of improvement of the application nonaqueous electrolytic solution, the application barbital acid compounds are in following compound
At least one, but not limited to this:
As a kind of improvement of the application nonaqueous electrolytic solution, the application barbital acid compounds are selected from formula (I -1) to formula
At least one of (I -17) described compound, but not limited to this.As a kind of improvement of the application nonaqueous electrolytic solution, the application
Mass percentage of the barbital acid compounds in nonaqueous electrolytic solution is 0.01%~3%.When barbital acid compounds
Content be lower than 0.01% when, complete and effective CEI film cannot be formed in positive electrode surface, to not can effectively prevent non-water power
Solve side reaction caused by the electronics transfer between liquid and electrode；And when barbiturates kind compound content is greater than 3%, meeting exists
Cathode surface forms thicker CEI film, causes lithium ion mobility resistance to increase, is unfavorable for the positive interface of battery in cyclic process
Stability.
It is further preferred that mass percentage range of the application barbital acid compounds in nonaqueous electrolytic solution
The upper limit optionally from 3%, 2.8%, 2.5%, 2.0%, 1.5%, 1.0%, lower limit optionally from 0.01%, 0.02%, 0.03%,
0.05%, 0.1%, 0.3%, 0.5%, 0.6%, 0.8%.It is further preferred that the barbital acid compounds are non-
Percentage composition in water electrolysis liquid is 0.05%~2%.
Preferably, mass percentage of the application barbital acid compounds in nonaqueous electrolytic solution is 1%.
As a kind of improvement of the application nonaqueous electrolytic solution, the application organic solvent includes cyclic carbonate, chain carbonic acid
At least one of ester and carboxylate；Wherein,
Cyclic carbonate is selected from ethylene carbonate (EC), propene carbonate (PC), gamma-butyrolacton, fluorinated ethylene carbonate
At least one of；
Linear carbonate be selected from dimethyl carbonate (DMC), butylene, diethyl carbonate (DEC), dipropyl carbonate,
At least one of methyl ethyl carbonate (EMC), methyl propyl carbonate, ethyl propyl carbonic acid ester；
Carboxylate be selected from methyl formate, Ethyl formate, propyl formate, methyl acetate, ethyl acetate (EA), propyl acetate,
At least one of methyl propionate, ethyl propionate, propyl propionate (PP), methyl butyrate, ethyl butyrate.
As a kind of improvement of the application nonaqueous electrolytic solution, the application electrolytic salt is in organic lithium salt or inorganic lithium salt
At least one.
As a kind of improvement of the application nonaqueous electrolytic solution, contain nitrogen, element sulphur, fluorine member in the application electrolytic salt
At least one of element, boron element, P elements.
As a kind of improvement of the application nonaqueous electrolytic solution, the application electrolytic salt is selected from lithium hexafluoro phosphate LiPF6, double three
Fluoromethane sulfimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), bis- (fluorine sulphonyl) imine lithium Li (N (SO2F)2) (be abbreviated as
LiFSI), di-oxalate lithium borate LiB (C2O4)2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4) (be abbreviated as
At least one of LiDFOB).
The application further relates to a kind of lithium ion battery, including positive plate, negative electrode tab, is arranged at intervals at positive plate and negative electrode tab
Between isolation film and electrolyte；The electrolyte is nonaqueous electrolytic solution described in aforementioned any one.
Present invention also provides a kind of lithium ion battery, including positive plate, negative electrode tab, it is arranged at intervals at positive plate and cathode
Isolation film, electrolyte and package foil between piece；The positive plate includes plus plate current-collecting body and is coated on plus plate current-collecting body
Positive diaphragm, negative electrode tab includes negative current collector and the cathode membrane that is coated on negative current collector；Before the electrolyte is
State nonaqueous electrolytic solution described in any one.
As a kind of improvement of the application lithium ion battery, the application anode diaphragm includes positive electrode active materials, binder
And conductive agent.
As a kind of improvement of the application lithium ion battery, the application positive electrode active materials are optionally from cobalt acid lithium LiCoO2、
At least one of lithium-nickel-manganese-cobalt ternary material, LiFePO4, LiMn2O4.
As a kind of improvement of the application lithium ion battery, the application positive electrode active materials are cobalt acid lithium and lithium-nickel-manganese-cobalt three
The mixture of first material.
As a kind of improvement of the application lithium ion battery, the application cathode membrane includes negative electrode active material, binder
And conductive agent.
As a kind of improvement of the application lithium ion battery, the application negative electrode active material is graphite and/or silicon.
Exemplary description is done below by way of technical solution of the specific embodiment to the application:
The preparation of electrolyte: in water content < 10ppm argon atmosphere glove box, preparation mixing nonaqueous solvents, then will fill
Divide dry lithium salts LiPF6It is dissolved in above-mentioned nonaqueous solvents, is made into LiPF6Concentration is the basic electrolyte of 1mol/L.
Composition and the mass ratio for mixing nonaqueous solvents are as shown in table 1.And according to shown in table 1, it is added in basic electrolyte
Barbital acids compound additive.
Example as barbital acid compounds are as follows: 1,3- dimethyl barbituric acid (B1, as shown in formula I -1), 1,3-
Dibutyl barbiturates (B2, as shown in formula I -4), 1,3- diphenyl barbituric acid (B3, as shown in formula I -5), 1,3- dimethyl -
2- thiobarbituricacidα- (B4, as shown in formula I -11), 1,3- dimethyl -5- amino -2- thiobarbituricacidα- (B5, such as I -8 institute of formula
Show).
The preparation of lithium ion battery:
1) preparation of positive plate: by positive active material cobalt acid lithium (molecular formula LiCoO2), conductive agent acetylene black, bonding
Agent polyvinylidene fluoride (being abbreviated as PVDF) is by weight 96:2:2 in suitable N-Methyl pyrrolidone (being abbreviated as NMP) solvent
In be thoroughly mixed, form it into uniform anode sizing agent；This slurry is coated on plus plate current-collecting body Al foil, dries, is cold
Pressure, obtains positive plate.
2) preparation of negative electrode tab: negative electrode active material graphite, conductive agent acetylene black, binder butadiene-styrene rubber (are abbreviated as
SBR), thickener sodium carboxymethylcellulose (being abbreviated as CMC) is according to weight ratio 95:2:2:1 in suitable deionized water solvent
It is thoroughly mixed, forms it into uniform negative electrode slurry；This slurry is coated on negative current collector Cu foil, drying, cold pressing,
Obtain negative electrode tab.
3) isolation film: using PE porous polymer film as isolation film.
4) preparation of lithium ion battery: positive plate, isolation film, negative electrode tab are folded in order, and isolation film is made to be in anode
Play the role of isolation between piece and negative electrode tab, then winding obtains naked battery core；Naked battery core is placed in outer packing foil, it will be above-mentioned
The electrolyte prepared is injected into the battery after drying, by the processes such as Vacuum Package, standing, chemical conversion, shaping, i.e. completion lithium
The preparation of ion battery.
The electrolyte and lithium ion battery of embodiment 1~14 and comparative example 1~4 are prepared according to above-mentioned preparation method；Electricity
The parameter setting of additive and organic solvent is as shown in table 1 in solution liquid, and the percentage numerical value in table 1, which refers to, accounts for the total matter of electrolyte
The percentage of amount.
The electrolyte component parameter list of 1 embodiment 1~14 of table and comparative example 1~4
Lithium ion battery made from each comparative example of the application and embodiment will be tested for the property as experiment below.
Loop test
The lithium ion battery being prepared is subjected to following tests respectively:
At 45 DEG C, by lithium ion battery, with 1C constant-current charge to 4.4V, then constant-voltage charge to electric current is 0.05C, then
So repeatedly cycle charging/electric discharge is carried out according to above-mentioned condition, respectively at this time to recycle for the first time with 1C constant-current discharge to 3.0V
The capacity retention ratio after lithium ion battery recycles 50 times, 100 times, 300 times is calculated.Every group of each 5 battery, wherein circulation
Capacity retention ratio afterwards is calculated according to the following formula.Selected electrolyte and obtained correlative measurement in each lithium ion battery
Data are tried referring to table 2.
Capacity retention ratio after circulation=(discharge capacity of corresponding circulation/discharge capacity recycled for the first time) × 100%, it follows
The results are shown in Table 2 for ring test.
Capacity retention ratio after the lithium ion battery of 2 embodiment 1~14 of table and comparative example 1~4 circulation
It can be seen that compared with comparative example 1 in conjunction in Tables 1 and 2, barbiturates be added in the electrolyte of embodiment 1-8
Class compound can improve the cycle performance of lithium ion battery.Because barbital acid compounds can be with during initial charge
It generates SEI film, can effectively prevent influence of the PC to anode.Compared with comparative example 2,1% is added in the electrolyte of embodiment 9-14
When barbital acid compounds, the cycle performance of lithium ion battery also has improvement.In embodiment 9~13, add in electrolyte
Enter mass fraction be 1% 1,3- dimethyl barbituric acid, 1,3- dibutyl barbiturates, 1,3- diphenyl barbituric acid, 1,
3- dimethyl -2- thiobarbituricacidα- and 1, when 3- dimethyl -5- amino -2- thiobarbituricacidα-, the cycle performance of battery is aobvious
It writes and is promoted.
The application other embodiments:
According to the electrolyte and lithium battery of the method preparation embodiment 15~31 of previous embodiment, difference is: electrolyte
Middle additive component and adding proportion are as shown in table 3:
3 embodiment of table, 15~31 battery electrolyte additive component and adding proportion
The performance for the battery being prepared is detected according to the method for previous embodiment, detection obtains embodiment battery
15~31 performance is similar to above embodiments, repeats no more as space is limited.
It is not for limiting claim, any this field skill although the application is disclosed as above with preferred embodiment
Art personnel without departing from the concept of this application, can make several possible variations and modification, therefore the application
Protection scope should be subject to the range that the claim of this application is defined.
Claims (9)
1. a kind of nonaqueous electrolytic solution, including organic solvent, electrolytic salt and additive, which is characterized in that contain in the additive
There are barbital acid compounds；
It is at least one of formula (I) compound represented that the barbital acid compounds, which are selected from structural formula,
Wherein,
R11、R12It is each independently selected from substituted or unsubstituted C1~12Alkyl, substituted or unsubstituted C6~26Aryl；
R13、R14It is each independently selected from hydrogen, amino, substituted or unsubstituted C1~12Alkyl, substituted or unsubstituted C6~26Virtue
Base ,-NH-R ', wherein R ' is substituted or unsubstituted C1~12Alkyl amine group；
X is selected from O and S；
Substituent group is selected from halogen；
Mass percentage of the barbital acid compounds in the nonaqueous electrolytic solution is 0.01%~3%.
2. nonaqueous electrolytic solution according to claim 1, which is characterized in that wherein,
R11、R12It is each independently selected from substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl；
R13、R14It is each independently selected from hydrogen, substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl, amino.
3. nonaqueous electrolytic solution according to claim 2, which is characterized in that the barbital acid compounds are selected from followingization
At least one of object is closed,
4. nonaqueous electrolytic solution according to claim 3, which is characterized in that the barbital acid compounds are described non-aqueous
Mass percentage in electrolyte is 0.05%~2%.
5. nonaqueous electrolytic solution according to claim 1, which is characterized in that the organic solvent includes cyclic carbonate, chain
At least one of shape carbonic ester and carboxylate.
6. nonaqueous electrolytic solution according to claim 5, which is characterized in that
The cyclic carbonate in ethylene carbonate, propene carbonate, fluorinated ethylene carbonate, butylene at least
It is a kind of；
The linear carbonate be selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate,
At least one of ethyl propyl carbonic acid ester；
The carboxylate is selected from methyl formate, Ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, propionic acid
At least one of methyl esters, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate.
7. nonaqueous electrolytic solution according to claim 1, which is characterized in that contain nitrogen, sulphur member in the electrolytic salt
At least one of element, fluorine element, boron element, P elements.
8. nonaqueous electrolytic solution according to claim 1, which is characterized in that the electrolytic salt is selected from lithium hexafluoro phosphate
LiPF6, double trifluoromethanesulfonimide lithium LiN (CF3SO2)2, bis- (fluorine sulphonyl) imine lithium Li (N (SO2F)2), double oxalic acid boric acid
Lithium LiB (C2O4)2, difluorine oxalic acid boracic acid lithium LiBF2(C2O4At least one of).
9. a kind of lithium ion battery, including positive plate, negative electrode tab, the isolation film being arranged at intervals between positive plate and negative electrode tab,
And electrolyte, which is characterized in that the electrolyte is any nonaqueous electrolytic solution of claim 1~8.
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| CN106654370A (en) * | 2016-11-30 | 2017-05-10 | 宁德时代新能源科技股份有限公司 | Non-aqueous electrolyte and lithium ion battery |
| CN106410279A (en) * | 2016-11-30 | 2017-02-15 | 宁德时代新能源科技股份有限公司 | Electrolyte and secondary battery |
| CN109830749B (en) | 2019-01-25 | 2021-06-04 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
| US20220181695A1 (en) * | 2019-03-29 | 2022-06-09 | Panasonic Intellectual Property Management Co., Ltd. | Non-aqueous electrolyte secondary battery |
| CN110994021A (en) * | 2019-11-19 | 2020-04-10 | 惠州市豪鹏科技有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
| CN111477961B (en) * | 2020-05-29 | 2022-10-28 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery containing non-aqueous electrolyte |
| CN112201855B (en) * | 2020-10-19 | 2022-04-01 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| CN114430068B (en) * | 2020-10-29 | 2024-01-23 | 深圳市研一新材料有限责任公司 | Lithium ion battery electrolyte |
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| WO2014133107A1 (en) * | 2013-02-27 | 2014-09-04 | 三菱化学株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte battery using same |
| DE102015008360A1 (en) * | 2015-06-27 | 2015-12-17 | Daimler Ag | Electrochemical energy storage |
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