CN109546222A - Aluminum honeycomb energy storage device electrolyte, aluminum honeycomb energy storage device and preparation method thereof - Google Patents
Aluminum honeycomb energy storage device electrolyte, aluminum honeycomb energy storage device and preparation method thereof Download PDFInfo
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- CN109546222A CN109546222A CN201811432684.7A CN201811432684A CN109546222A CN 109546222 A CN109546222 A CN 109546222A CN 201811432684 A CN201811432684 A CN 201811432684A CN 109546222 A CN109546222 A CN 109546222A
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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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
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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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- 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
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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
The invention discloses a kind of aluminum honeycomb energy storage device electrolyte, aluminum honeycomb energy storage device and preparation method thereof, are related to electrochemical energy storing device technical field.Aluminum honeycomb energy storage device electrolyte includes lithium salts and organic solvent, and organic solvent includes 10-20vol% ring-type esters solvent and 80-90vol% line style esters solvent.The present invention alleviate existing electrolyte tie up in Al cathode system influence battery capacity play, the cycle performance of battery it is poor, and the preferable system of normal temperature circulation, cryogenic property is again poor.Low-temperature electrolyte provided by the invention and Al cathode system matching are good, low viscosity is able to maintain under low temperature, system is set to have higher conductivity, cathode-electrolyte has lower solid liquid interface impedance simultaneously, so that lithium ion is effectively deviate from, the low temperature charge-discharge performance of Al negative electrode lithium ion energy storage device can be significantly improved using the electrolyte.
Description
Technical field
The present invention relates to electrochemical energy storing device technical fields, are electrolysed in particular to a kind of aluminum honeycomb energy storage device
Liquid, aluminum honeycomb energy storage device and preparation method thereof.
Background technique
Since commercialization, high-energy density, self discharge is small, output voltage is high and the advantage that has extended cycle life etc. is prominent
Lithium ion battery occupy rapidly mobile phone, laptop etc. be representative consumer electronics product field nearly all city
, in recent years electric bicycle, in terms of application also show geometric growth.But with application and
The increasingly increase of demand, disadvantage of the lithium ion battery on cryogenic property also more highlight.- 30 DEG C and discharge capacity below
The 50-60% of 25 DEG C of discharge capacities is only accounted for, it is even lower, seriously constrain the use of north of china in winter electric car.
In the prior art, patent CN107171023A discloses a kind of low temperature electrolytes for Li-ion batteries, and solvent is by carbonic acid
Vinyl acetate, dimethyl carbonate, fluoropropylene carbonate and chlorocarbonic acid acrylic ester are constituted, the volume ratio of four kinds of materials be (45~
49): (45~49): (1~5): (1~7), solute LiPF6And LiBF4Mixing lithium salts.The carbonic acid replaced using two kinds of halogens
Acrylic ester (PC) material solves the inlay effect of PC as electrolyte solvent；Electrolyte fusing point is reduced, electrolyte is improved and stablizes
Property, -20 DEG C and capacity retention ratio at -30 DEG C are respectively 84.5% and 74.2%.
However existing cryogenic technique is all the graphite cathode system more mature applied to development, with Al cathode system
Matching degree is not high, and existing electrolyte ties up in Al cathode system the capacity performance and the cyclicity of battery for influencing battery
Can be also poor, and the preferable system of normal temperature circulation, cryogenic property and poor, especially -30 DEG C of discharge capacity.
It is therefore desired to provide a kind of and matched low-temperature electrolyte of Al cathode system, it is able to solve the above problem
At least one of.
In view of this, the present invention is specifically proposed.
Summary of the invention
One of the objects of the present invention is to provide a kind of aluminum honeycomb energy storage device electrolyte, can alleviate above-mentioned technical problem
At least one of.
The second object of the present invention is to provide a kind of preparation method of above-mentioned aluminum honeycomb energy storage device electrolyte, method letter
It is single.
The third object of the present invention is to provide a kind of aluminum honeycomb energy storage device, including the electrolysis of above-mentioned aluminum honeycomb energy storage device
Electrolyte made from the preparation method of liquid or above-mentioned aluminum honeycomb energy storage device electrolyte has and above-mentioned aluminum honeycomb energy storage device electricity
Solve the identical advantage of liquid.
The fourth object of the present invention is to provide the preparation method of above-mentioned aluminum honeycomb energy storage device, simple production process, at
This is low.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
In a first aspect, the present invention provides a kind of aluminum honeycomb energy storage device electrolyte, including lithium salts and organic solvent, it is described
Organic solvent includes 10-20vol% ring-type esters solvent and 80-90vol% line style esters solvent.
Preferably, based on the technical solution of the present invention, the organic solvent includes that 15-20vol% ring-type esters are molten
Agent and 80-85vol% line style esters solvent；
Preferably, the organic solvent includes 20vol% ring-type esters solvent and 80vol% line style esters solvent.
Preferably, based on the technical solution of the present invention, molar concentration of the lithium salts in the organic solvent is
0.1-10mol/L, preferably 1-2mol/L；
Preferably, lithium salts includes LiCoO2、LiBF4、LiPF6、LiTFSI、LiNO3、Li2CO3、LiCl、LiCF3SO3、
LiPF3(C2F5)3、LiPF4(C2O4)、LiN(CF3SO2)2、LiFSI、LiFAP、LiClO4, LiBOB, LiDFOB, LTBP or
LiAsF6One or more of, preferably LiPF6。
Preferably, based on the technical solution of the present invention, the electrolyte further includes additive, and the additive adds
Dosage accounts for the 0.01-20wt% of the lithium salts and the organic solvent total amount, preferably 5-20wt%, further preferred 5-
10wt%；
Preferably, the additive includes fluorinated ethylene carbonate and/or vinylene carbonate.
Preferably, based on the technical solution of the present invention, the cyclic annular esters solvent include cyclic carbonates and/or
Cyclic carboxylic acids esters preferably include ethylene carbonate and/or propene carbonate.
Preferably, based on the technical solution of the present invention, the line style esters solvent include linear carbonate class and/or
Line style carboxylic acid esters preferably include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate, butyl acetate, propionic acid
One of methyl esters or ethyl propionate or at least two.
Second aspect, the present invention provides a kind of preparation method of above-mentioned aluminum honeycomb energy storage device electrolyte, including it is following
Step: lithium salts, organic solvent and additive are uniformly mixed, and obtain aluminum honeycomb energy storage device electrolyte.
Preferably, based on the technical solution of the present invention, the preparation method of above-mentioned aluminum honeycomb energy storage device electrolyte, packet
It includes following steps: cyclic annular esters solvent and line style esters solvent is mixed in proportion, obtain solvent after adding additive mixing；
Then 0-15 DEG C of addition lithium salts of temperature is kept after the drying of lithium type molecular sieve is added, obtains aluminum honeycomb energy storage device electrolyte.
The third aspect, the present invention provides a kind of aluminum honeycomb energy storage devices, including above-mentioned aluminum honeycomb energy storage device electrolyte
Or electrolyte made from the preparation method of above-mentioned aluminum honeycomb energy storage device electrolyte.
Fourth aspect, the present invention provides a kind of preparation methods of above-mentioned aluminum honeycomb energy storage device, comprising the following steps: will
Cathode, diaphragm, anode and the aluminum honeycomb energy storage device electrolyte are assembled, and aluminum honeycomb energy storage device is obtained.
Compared with the prior art, the invention has the following beneficial effects:
(1) organic solvent that electrolyte of the invention uses includes 10-20vol% ring-type esters solvent and 80-90vol%
Line style esters solvent, the electrolyte and Al cathode energy storage device (such as Al negative electrode lithium ion battery) matching are good, energy under low temperature
Low viscosity is enough kept, so that system is had higher conductivity, while cathode-electrolyte has lower solid liquid interface impedance, makes lithium
Ion can effectively be deviate from, and the low temperature charge-discharge performance of Al negative electrode lithium ion energy storage device can be significantly improved using the electrolyte.
(2) use discharge capacity of the lithium ion battery made of electrolyte of the present invention when temperature is down to -30 DEG C for room temperature
72% or more of (25 DEG C) discharge capacity.
(3) aluminum honeycomb energy storage device of the invention includes the electrolyte of aforementioned present invention, is had identical as above-mentioned electrolyte
Advantage, the discharge property of energy storage device at low temperature can be obviously improved by using the electrolyte of low viscosity, low interface impedance
Energy.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to the first aspect of the invention, a kind of aluminum honeycomb energy storage device electrolyte is provided, including lithium salts and organic
Solvent, organic solvent include 10-20vol% ring-type esters solvent and 80-90vol% line style esters solvent.
Aluminum honeycomb energy storage device refers to that the energy storage device for making cathode with aluminium, aluminium serve as negative electrode active material and negative current collector,
Here aluminium includes but is not limited to fine aluminium, is also possible to aluminium alloy.Illustrative energy storage device may include secondary cell, mixing
Supercapacitor etc..
Illustrative aluminum honeycomb energy storage device includes that for example, aluminium foil negative electrode lithium ion battery, aluminium foil-graphite double ion is electric
Pond (using graphite as anode, using aluminium foil simultaneously as cathode and collector) or aluminium foil negative electrode lithium ion mixed capacitor etc..
Cyclic annular esters solvent refers to a kind of esters solvent in structure with ring structure, typical but non-limiting for example to wrap
Cyclic carbonates and/or cyclic carboxylic acids esters are included, illustrative ring-type esters solvent is, for example, ethylene carbonate (Ethylene
Carbonate, EC) or propene carbonate (Propylene carbonate, PC) etc..
Line style esters solvent refers to a kind of esters solvent in structure in line style, typical but non-limiting for example including line
Type carbonates and/or line style carboxylic acid esters, illustrative line style esters solvent are, for example, dimethyl carbonate (Dimethyl
Carbonate, DMC), diethyl carbonate (Diethyl carbonate, DEC), methyl ethyl carbonate (Ethyl Methyl
Carbonate, EMC), ethyl acetate (ethyl acetate, EA), butyl acetate (n-Butyl acetate, BA), propionic acid first
Ester (Methyl Propionate, MP) or ethyl propionate (Ethyl Propionate, EP) etc..
On the basis of organic solvent, including 10-20vol% ring-type esters solvent and 80-90vol% line style esters solvent.
The percent by volume of illustrative ring-type esters solvent is, for example, 10%, 15% or 20%；Illustrative linear ester
The percent by volume of class solvent is, for example, 80%, 85% or 90%.
The type of lithium salts is not construed as limiting, as long as lithium ion can be dissociated into, such as can be using conventional lithium salts.Show
The lithium salts of example property is, for example, LiCoO2、LiPF6, LiTFSI (double trifluoromethanesulfonimide lithiums), LiBF4、LiNO3、Li2CO3、
LiCl、LiN(CF3SO2)2(two (trimethyl fluoride sulfonyl) imine lithiums), LiCF3SO3(trifluoromethyl sulfonic acid lithium), LiPF3(C2F5)3
(perfluoroalkyl phosphate lithium), LiPF4(C2O4) (tetrafluoro oxalic acid lithium phosphate), LiFAP, LiFSI, LiClO4, LiBOB (double oxalic acid boron
Sour lithium), LiDFOB, LTBP (three (catechol) lithium phosphates) or LiAsF6Deng.
Lithium-ion energy storage device is in cryogenic property especially when temperature reaches -30 DEG C and following discharge performance can be compared with room temperature
More than drop by half, this is because under cryogenic, being on the one hand electrolysed fluid viscosity can increased dramatically, cause under system conductivity
Drop, charge transfer impedance rise, and influence cell discharge performance；Another aspect cathode-electrolyte interface impedance increases so that lithium from
Son cannot effectively be deviate from, to influence discharge capacity.
The organic solvent of electrolyte of the present invention passes through the cyclic annular esters solvent and line style esters solvent of certain volume percentage
Be used cooperatively, make to be able to maintain low viscosity under its low temperature, so that system is had higher conductivity, while cathode-electrolyte has
Lower solid liquid interface impedance, enables lithium ion effectively to deviate from.Electrolyte of the invention is a kind of low viscosity, low interface impedance
Low-temperature electrolyte, it is good with the energy storage device matching of Al cathode system, energy storage device putting at low temperature can be obviously improved
Electrical property.Discharge capacity of the lithium ion battery made of the electrolyte when temperature is down to -30 DEG C is used to put for room temperature (25 DEG C)
72% or more of capacitance.
In one embodiment, organic solvent includes 15-20vol% ring-type esters solvent and 80-85vol% linear ester
Class solvent.
In one embodiment, organic solvent includes that 20vol% ring-type esters solvent and 80vol% line style esters are molten
Agent.
The cyclic annular esters solvent and line style esters solvent of the percent by volume be used cooperatively, and makes energy storage device at low temperature
Discharge performance is more preferable.
In one embodiment, the molar concentration of lithium salts in organic solvent is 0.1-10mol/L, preferably 1-
2mol/L。
The illustrative concentration of lithium salts be, for example, 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.7mol/L, 0.8mol/L,
1mol/L, 2mol/L, 5mol/L or 10mol/L.
Ion concentration influences the ion transmission performance of electrolyte, and lithium salt is too low in electrolyte, Li+Very few, ion passes
Defeated performance is poor, and conductivity is low, and lithium salt is excessively high in electrolyte, Li+Excessively, the degree of the viscosity of electrolyte and ion association
It can increase with lithium salt and increase, this can reduce conductivity again.
In one embodiment, electrolyte further includes additive, and the additive amount of additive accounts for lithium salts and organic solvent is total
The 0.01-20wt% of amount, preferably 5-20wt%, further preferred 5-10wt%；
The type of additive is not construed as limiting, such as may include the common conventional additives of field of lithium ion battery.Example
Such as conventional film for additive, additives for overcharge protection additive, stabilizer, additive, the conductive additive for improving high temperature performance
Or flame-retardant additive etc..
Illustrative additive is, for example, fluorinated ethylene carbonate, vinylethylene carbonate, vinylene carbonate, 1,4- fourth
Sultones, 1,3- propane sultone, sulfuric acid vinyl ester, ethyl sulfate, sulfuric acid acrylic ester, ethylene sulfite, sulfurous acid
Acrylic ester, dimethyl sulfite, diethyl sulfite, glycol sulfite, methyl chlorocarbonate, methyl phenyl ethers anisole, dimethyl
Sulfoxide, diazine, metadiazine, acetamide, 4- fluoroanisole, fluoro chain ether, difluoromethyl ethylene carbonate, hat
Ether 12-crown-4, crown ether 18- crown- 6, chlorocarbonic acid vinyl acetate, trifluoromethy ethylene carbonate, bromo ethylene carbonate, bromo
Butyrolactone, trifluoroethyl phosphonic acids, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, ethanol amine, cyclobutyl sulfone, carbonization
Dimethylamine, 1,3- dioxolanes, acetonitrile, long-chain olefin, sodium carbonate, lithium carbonate, calcium carbonate, sulfur dioxide or carbon dioxide
Deng.
On the basis of lithium salts and organic solvent total amount, the illustrative mass fraction of additive is, for example, the additive amount of additive
0.01%, 0.2%, 0.4%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%,
14%, 15%, 16%, 17%, 18%, 19% or 20%.
By adding the additive of certain content, certain thickness SEI film is formed, aluminum honeycomb expansion is alleviated.
In one embodiment, additive includes fluorinated ethylene carbonate and/or vinylene carbonate.
According to the second aspect of the invention, a kind of preparation method of above-mentioned aluminum honeycomb energy storage device electrolyte is provided,
The following steps are included:
Lithium salts, organic solvent and additive are uniformly mixed, aluminum honeycomb energy storage device electrolyte is obtained.
The preparation method of aluminum honeycomb energy storage device electrolyte of the present invention is simple and convenient to operate, and can carry out mass production.
In one embodiment, the preparation method of aluminum honeycomb energy storage device electrolyte, comprising the following steps:
Cyclic annular esters solvent and line style esters solvent are mixed in proportion, obtain solvent after adding additive mixing；So
0-15 DEG C of addition lithium salts of temperature is kept after the drying of lithium type molecular sieve is added afterwards, obtains aluminum honeycomb energy storage device electrolyte.
Electrolyte removes moisture removal through the drying of lithium type molecular sieve, good compared with lithium salt electrolyte stability is added under low temperature.
According to the third aspect of the present invention, a kind of aluminum honeycomb energy storage device, including above-mentioned aluminum honeycomb accumulator are provided
Electrolyte made from the preparation method of part electrolyte or above-mentioned aluminum honeycomb energy storage device electrolyte.
Illustrative aluminum honeycomb energy storage device is, for example, aluminum honeycomb secondary cell or aluminum honeycomb capacitor etc..
Aluminum honeycomb energy storage device has and above-mentioned electrolysis liquid phase due to using above-mentioned aluminum honeycomb energy storage device electrolyte
Same advantage, can be obviously improved the electric discharge of energy storage device at low temperature by using the electrolyte of low viscosity, low interface impedance
Performance.
A kind of illustrative aluminum honeycomb secondary cell includes cathode, anode, the diaphragm between positive and negative anodes and above-mentioned
Electrolyte.
Illustrative cathode is aluminium foil.
Illustrative anode includes plus plate current-collecting body and positive electrode, is not construed as limiting to positive electrode, can using lithium from
The positive electrode or Dual-ion cell positive electrode of sub- field of batteries routine.The active material of positive electrode is can be reversibly embedding
Enter, the material of deintercalate lithium ions or anion.
Illustratively can reversibly be embedded in, the material of deintercalate lithium ions be lithium ion battery conventional cathode material, such as
For LiFePO4, cobalt acid lithium, LiMn2O4, nickel-cobalt-manganese ternary material or lithium-rich anode material etc..
It illustratively can reversibly be embedded in, the material of deintercalation electrolysis solution anion is Dual-ion cell positive electrode, example
The for example stratified materials such as graphite carbon material, sulfide, carbide, nitride or oxide.
It is understood that being not construed as limiting to plus plate current-collecting body, illustrative plus plate current-collecting body is, for example, aluminium.
It in one embodiment, further include conductive agent and binder in positive electrode.
It is understood that conductive agent and binder it is not also specifically limited, the conductive agent of this field routine can be used
And binder.
Illustrative conductive agent is, for example, electrically conductive graphite, conductive black, carbon fiber, conductive carbon ball, carbon nanotube or graphite
One or more of alkene.
Illustrative binder is, for example, carboxymethyl cellulose, polytetrafluoroethylene (PTFE), Kynoar, polyvinyl alcohol, SBR rubber
One or more of glue or polyolefins (polyvinyl chloride, polybutadiene, polyisoprene etc.).
The ratio of the active material of positive electrode, conductive agent and binder is not construed as limiting, it is preferable that positive electrode includes
The binder of the active material of the positive electrode of 60-97wt%, the conductive agent of 1-30wt% and 2-10wt%.
Electrolyte as described in electrolyte in description and first aspect describes identical.
It is understood that diaphragm is it is not also specifically limited, using this field conventional separator.
Diaphragm can be porous polymer film, be also possible to inorganic porous film, illustrative diaphragm is for example including glass
Glass fiber, porous polyethylene film, porous polypropylene film, porous compound polymer film, porous ceramics diaphragm or non-woven fabrics
One or more of.
It is understood that be not construed as limiting to the form of aluminum honeycomb secondary cell, including but not limited to square, it is plate,
The forms such as Coin shape, cylindrical type, button type, Soft Roll or laminated type.The size of aluminum honeycomb secondary cell is not construed as limiting, can be
Compact battery is also possible to the large-sized battery of electric vehicle etc..
According to the fourth aspect of the present invention, a kind of preparation method of above-mentioned aluminum honeycomb energy storage device is provided, including with
Lower step:
Anode, cathode, diaphragm and aluminum honeycomb energy storage device electrolyte are assembled, aluminum honeycomb energy storage device is obtained.
It is understood that anode, cathode, diaphragm and electrolyte assembling mode be not particularly limited, routine can be used
Assembling mode carry out.
It is the preparation method simple process of aluminum honeycomb secondary cell, at low cost.
In one embodiment, the preparation method of aluminum honeycomb secondary cell, comprising the following steps:
(a) active material of positive electrode, conductive agent and binder and solvent preparation anode: are mixed and made into slurry；Again
Slurry is evenly applied to plus plate current-collecting body surface, trimming, cut-parts and slitting after drying obtain the anode of required size；
(b) it prepares cathode: by the trimming of cathode aluminium foil, cut-parts and slitting, obtaining the cathode of required size；
(c) it prepares electrolyte: cyclic annular esters solvent and line style esters solvent is mixed in proportion, add additive mixing
After obtain solvent；Then 0-15 DEG C of addition lithium salts of temperature is kept after the drying of lithium type molecular sieve is added, obtains electrolyte；
(d) it prepares diaphragm: diaphragm is cut into required size, cleaning and drying；
Anode, cathode, electrolyte and diaphragm are assembled, aluminum honeycomb secondary cell is obtained.
As long as the sequence of step or the sequence for carrying out certain movements are inessential it should be understood that keeping method can operate.Separately
Outside, two or more steps or movement can be carried out simultaneously.
The present invention is further illustrated below by specific embodiment and comparative example, it should be understood, however, that, these implementations
Example, which is only used for being described in more detail, to be used, and but should not be understood as present invention is limited in any form.
Embodiment 1
A kind of low-temperature electrolyte, comprising: lithium salts LiPF6, organic solvent includes the fluorinated ethylene carbonate of 10vol%
(FEC), the propene carbonate (PC) of 10vol%, the diethyl carbonate (DEC) of 40vol% and the methyl ethyl carbonate rouge of 40vol%
(EMC) (benchmark is organic solvent, and for 100%), additive is vinylene carbonate (VC) and fluorinated ethylene carbonate
(FEC), the molar concentration of lithium salts in organic solvent is 1mol/L, and fluorinated ethylene carbonate (FEC) is in lithium salts and organic solvent
In mass percentage be 5%, mass percentage of the vinylene carbonate (VC) in lithium salts and organic solvent be 5%.
The preparation method of low-temperature electrolyte, comprising the following steps:
FEC, PC, DEC and EMC are mixed in proportion, 5% is respectively separately added and (accounts for lithium salts and organic solvent is total
The mass ratio of sum) FEC and VC as additive, electrolyte solvent is obtained after mixing, the lithium type point of 10% (mass ratio) is added
The dry LiPF for keeping 0-15 DEG C of temperature addition 1mol/L afterwards for 24 hours of son sieve6, obtain low-temperature electrolyte.
Embodiment 2
A kind of low-temperature electrolyte, comprising: lithium salts LiPF6, organic solvent include 10vol% ethylene carbonate (EC),
The methyl ethyl carbonate (EMC) of 40vol%, the dimethyl carbonate (DMC) of 10vol%, 10vol% carbonic acid diethyl ester (DEC) and
(benchmark is organic solvent to the ethyl propionate (EP) of 30vol%, and for 100%), additive is vinylene carbonate (VC) and fluorine
For ethylene carbonate (FEC), the molar concentration of lithium salts in organic solvent is 1mol/L, and fluorinated ethylene carbonate (FEC) is in lithium
Mass percentage in salt and organic solvent is 5%, quality hundred of the vinylene carbonate (VC) in lithium salts and organic solvent
Dividing content is 5%.
The preparation method of low-temperature electrolyte, comprising the following steps:
EC, EMC, DMC, DEC and EP are mixed in proportion, 5% is respectively separately added and (accounts for lithium salts and organic solvent
The mass ratio of summation) FEC and VC mixed as additive after obtain electrolyte solvent, the lithium type point of 10% (mass ratio) is added
The dry LiPF for keeping 0-15 DEG C of temperature addition 1mol/L afterwards for 24 hours of son sieve6, obtain low-temperature electrolyte.
Embodiment 3
A kind of low-temperature electrolyte, comprising: lithium salts LiPF6, organic solvent include 10vol% ethylene carbonate (EC),
The propene carbonate (PC) of 10vol%, the methyl ethyl carbonate (EMC) of 40vol%, 10vol% dimethyl carbonate (DMC),
(benchmark is organic solvent to the ethyl propionate (EP) of the carbonic acid diethyl ester (DEC) of 20vol% and 10vol%, and 100%), to add
Adding agent is vinylene carbonate (VC) and fluorinated ethylene carbonate (FEC), and the molar concentration of lithium salts in organic solvent is 1mol/
L, mass percentage of the fluorinated ethylene carbonate (FEC) in lithium salts and organic solvent are 5%, and vinylene carbonate (VC) exists
Mass percentage in lithium salts and organic solvent is 5%.
The preparation method of low-temperature electrolyte, comprising the following steps:
EC, PC, EMC, DMC, DEC and EP are mixed in proportion, 5% is respectively separately added and (accounts for lithium salts and organic
The mass ratio of solvent summation) FEC and VC mixed as additive after obtain electrolyte solvent, the lithium of 10% (mass ratio) is added
The dry LiPF for keeping 0-15 DEG C of temperature addition 1mol/L afterwards for 24 hours of type molecular sieve6, obtain low-temperature electrolyte.
Embodiment 4
A kind of low-temperature electrolyte, comprising: lithium salts LiPF6, organic solvent include 20vol% ethylene carbonate (EC),
Butyl acetate (BA) (benchmark of the methyl ethyl carbonate (EMC) of 40vol%, the diethyl carbonate (DEC) of 10vol% and 30vol%
For organic solvent, and for 100%), additive is that vinylene carbonate (VC) and fluorinated ethylene carbonate (FEC), lithium salts are having
Molar concentration in solvent is 1mol/L, and quality percentage of the fluorinated ethylene carbonate (FEC) in lithium salts and organic solvent contains
Amount is 5%, and mass percentage of the vinylene carbonate (VC) in lithium salts and organic solvent is 5%.
The preparation method of low-temperature electrolyte, comprising the following steps:
EC, EMC, DEC and BA are mixed in proportion, 5% is respectively separately added and (accounts for lithium salts and organic solvent summation
Mass ratio) FEC and VC mixed as additive after obtain electrolyte solvent, the lithium type molecular sieve of 10% (mass ratio) is added
The dry LiPF for keeping 0-15 DEG C of temperature addition 1mol/L afterwards for 24 hours6, obtain low-temperature electrolyte.
Embodiment 5
A kind of low-temperature electrolyte, comprising: lithium salts LiPF6, organic solvent include 5vol% ethylene carbonate (EC),
The propene carbonate (PC) of 5vol%, the methyl ethyl carbonate (EMC) of 50vol%, 20vol% diethyl carbonate (DEC) and
(benchmark is organic solvent to the butyl acetate (BA) of 20vol%, and for 100%), additive is vinylene carbonate (VC) and fluorine
For ethylene carbonate (FEC), the molar concentration of lithium salts in organic solvent is 1mol/L, and fluorinated ethylene carbonate (FEC) is in lithium
Mass percentage in salt and organic solvent is 5%, quality hundred of the vinylene carbonate (VC) in lithium salts and organic solvent
Dividing content is 5%.
The preparation method of low-temperature electrolyte, comprising the following steps:
EC, PC, EMC, DEC and BA are mixed in proportion, 5% is respectively separately added and (accounts for lithium salts and organic solvent
The mass ratio of summation) FEC and VC mixed as additive after obtain electrolyte solvent, the lithium type point of 10% (mass ratio) is added
The dry LiPF for keeping 0-15 DEG C of temperature addition 1mol/L afterwards for 24 hours of son sieve6, obtain low-temperature electrolyte.
Embodiment 6
The present embodiment and the difference of embodiment 5 are that the percent by volume that EC, PC, EMC, DEC and BA occupy solvent is
EC:PC:EMC:DEC:BA=10%:5%:45%:20%:20%.
Embodiment 7
The difference for applying example and embodiment 5 is that the percent by volume that EC, PC, EMC, DEC and BA occupy solvent is EC:
PC:EMC:DEC:BA=10%:10%:50%:20%:20%.
Embodiment 8
A kind of low-temperature electrolyte, comprising: lithium salts LiPF6, organic solvent include 20vol% ethylene carbonate (EC),
The methyl ethyl carbonate (EMC) of 30vol%, the diethyl carbonate (DEC) of 10vol%, 20vol% ethyl acetate (EA) and
(benchmark is organic solvent to the butyl acetate (BA) of 20vol%, and for 100%), additive is vinylene carbonate (VC) and fluorine
For ethylene carbonate (FEC), the molar concentration of lithium salts in organic solvent is 1mol/L, and fluorinated ethylene carbonate (FEC) is in lithium
Mass percentage in salt and organic solvent is 5%, quality hundred of the vinylene carbonate (VC) in lithium salts and organic solvent
Dividing content is 5%.
The preparation method of low-temperature electrolyte, comprising the following steps:
EC, EMC, DEC, EA and BA are mixed in proportion, 5% is respectively separately added and (accounts for lithium salts and organic solvent
The mass ratio of summation) FEC and VC mixed as additive after obtain electrolyte solvent, the lithium type point of 10% (mass ratio) is added
The dry LiPF for keeping 0-15 DEG C of temperature addition 1mol/L afterwards for 24 hours of son sieve6, obtain low-temperature electrolyte.
Embodiment 9
The present embodiment and the difference of embodiment 8 are that the percent by volume that EC, EMC, DEC, EA and BA occupy solvent is
EC:EMC:DEC:EA:BA=15%:35%:10%:20%:10%.
Embodiment 10
The present embodiment and the difference of embodiment 8 are that the percent by volume that EC, EMC, DEC, EA and BA occupy solvent is
EC:EMC:DEC:EA:BA=10%:40%:10%:20%:10%.
Comparative example 1
" a kind of double trifluoro ethoxies pair fluoboric acid lithium salts and the lithium-ion electric comprising it disclosed in patent CN107565166A
The low-temperature electrolyte of embodiment 2 in pond low-temperature electrolyte and lithium ion battery ".
It include: LiPF in low temperature electrolytes for Li-ion batteries6, ethylene carbonate (EC), methyl ethyl carbonate (EMC), carbonic acid
Diethylester (DEC), additive vinylene carbonate (VC) and the double fluoboric acid lithium salts of double trifluoro ethoxies.
By ethylene carbonate (EC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), additive vinylene carbonate
(VC) and the double fluoboric acid lithium salts of double trifluoro ethoxy, in mass ratio: EC:EMC:DEC:VC: the double lithium fluoroborates of double trifluoro ethoxies
Salt=30%:30%:37.9%:2%:0.1%, is mixed to get electrolyte solvent, dissolves in 1mol/L in the electrolyte solvent
LiPF6To get arrive nonaqueous electrolytic solution.
Comparative example 2
The low-temperature electrolytic of embodiment 1 in " a kind of low temperature electrolytes for Li-ion batteries " disclosed in patent CN107171023A
Liquid.
By ethylene carbonate, dimethyl carbonate, fluoropropylene carbonate and chlorocarbonic acid acrylic ester 45:45 by volume:
3:7 mixing, forms electrolyte solvent after stirring, then by LiPF6And LiBF4MLiPF in mass ratio6:mLiBF4The ratio of=8:1
It is dissolved in after mixing in above-mentioned solvent, in glove box after strong stirring, can be configured to the low-temperature electrolyte that concentration is 1.2mol/L.
Comparative example 3
Embodiment 5 is low in " a kind of using ethyl acetate as the low-temperature electrolyte of solvent " disclosed in patent CN106169611A
Warm electrolyte.
Under the conditions of anhydrous and oxygen-free, using ethyl acetate as solvent, will be bis- (trimethyl fluoride sulfonyl) imine lithium according to 2mol/L
Molar concentration be dissolved in wherein.
Test example
Embodiment 1-10 and the resulting low-temperature electrolyte of comparative example 1-3 are fabricated to Al negative electrode lithium ion battery, Al is negative
Pole lithium ion battery includes anode pole piece, diaphragm, cathode Al piece and embodiment 1-10 and the resulting low-temperature electrolytic of comparative example 1-3
Liquid；
The preparation method of Al negative electrode lithium ion battery the following steps are included:
Anode pole piece: by ternary material NCM523, Super P conductive agent, PVDF binder, KS-6 proportionally 96.5:
1:1.5:1 mixing is added suitable NMP and stirs to certain viscosity, the uniform Al foil surface for being coated in 20 μm, high temperature drying
The soldering polar ear after trimming, cut-parts, slitting afterwards, is made the anode pole piece of Al negative electrode lithium ion battery；
Welding Al-Ni tab obtains after the Al foil that cathode Al piece is 50 μm directly carries out trimming, cut-parts, slitting；
Diaphragm is Cangzhou jewel diaphragm；
Above-mentioned positive and negative anodes and diaphragm are passed through into winding process, dry battery core is made and is packed into steel shell, after welding nut cap, is put into 80 DEG C
Embodiment 1-10 and the resulting low-temperature electrolyte of comparative example 1-3 are separately injected after the dry 48h of vacuum oven, through sealing
After mouth, forming and capacity dividing, Al negative electrode lithium ion battery is obtained.
All of above operation carries out in glove box.
Low temperature performance and normal-temperature circulating performance test are carried out to obtained Al negative electrode lithium ion battery, test method is such as
Under:
Low temperature performance: it at 25 DEG C, tests battery and fills/filled after 0.5C constant-current discharge circulation 5 weeks with 0.5C constant current constant voltage
Full electricity, records its charging capacity.After battery is then shelved 4-16h under the conditions of -20 DEG C or -30 DEG C ± 2 DEG C, with 0.5C constant current
It is discharged to blanking voltage and records its discharge capacity, discharge capacity when calculating separately -20 DEG C and -30 DEG C is held with electric discharge at 25 DEG C
The percentage of amount；
500 weeks capacity retention ratios: it at 25 DEG C, tests battery and is filled/0.5C constant-current discharge circulation 500 weeks with 0.5C constant current constant voltage
After, record its capacity retention ratio.
The results are shown in Table 1.
The low temperature performance test of 1 aluminum honeycomb lithium ion battery of table and normal temperature circulation data
From table 1 it follows that using lithium ion battery made of electrolyte of the embodiment of the present invention when temperature is down to -30 DEG C
When discharge capacity be room temperature (25 DEG C) discharge capacity 72% or more, 500 weeks capacity retention ratios of battery are 80% or more.From right
Although as can be seen that linear carboxylate solvent can improve electrolyte cryogenic property in ratio, with the matching degree of Al cathode compared with
It is low, the normal-temperature circulating performance of battery is influenced, cyclic annular esters solvent and line style esters solvent within the scope of the present invention is used cooperatively
The normal-temperature circulating performance of battery can be improved while improving low temperature charge-discharge performance.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that wrapping in the following claims
Include all such changes and modifications belonged in the scope of the invention.
Claims (10)
1. a kind of aluminum honeycomb energy storage device electrolyte, which is characterized in that including lithium salts and organic solvent；The organic solvent includes
10-20vol% ring-type esters solvent and 80-90vol% line style esters solvent.
2. aluminum honeycomb energy storage device electrolyte described in accordance with the claim 1, which is characterized in that the organic solvent includes 15-
20vol% ring-type esters solvent and 80-85vol% line style esters solvent；
Preferably, the organic solvent includes 20vol% ring-type esters solvent and 80vol% line style esters solvent.
3. aluminum honeycomb energy storage device electrolyte described in accordance with the claim 1, which is characterized in that the lithium salts is described organic molten
Molar concentration in agent is 0.1-10mol/L, preferably 1-2mol/L；
Preferably, lithium salts includes LiCoO2、LiBF4、LiPF6、LiTFSI、LiNO3、Li2CO3、LiCl、LiCF3SO3、LiPF3
(C2F5)3、LiPF4(C2O4)、LiN(CF3SO2)2、LiFSI、LiFAP、LiClO4, LiBOB, LiDFOB, LTBP or LiAsF6In
One or more, preferably LiPF6。
4. aluminum honeycomb energy storage device electrolyte described in accordance with the claim 1, which is characterized in that the electrolyte further includes addition
Agent, the additive amount of the additive account for the 0.01-20wt% of the lithium salts and the organic solvent total amount, preferably 5-20wt%,
Further preferred 5-10wt%；
Preferably, the additive includes fluorinated ethylene carbonate and/or vinylene carbonate.
5. according to the described in any item aluminum honeycomb energy storage device electrolyte of claim 1-4, which is characterized in that the ring-type esters
Solvent includes cyclic carbonates and/or cyclic carboxylic acids esters, preferably includes ethylene carbonate and/or propene carbonate.
6. according to the described in any item aluminum honeycomb energy storage device electrolyte of claim 1-4, which is characterized in that the line style esters
Solvent includes linear carbonate class and/or line style carboxylic acid esters, preferably includes dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate
One of ester, ethyl acetate, butyl acetate, methyl propionate or ethyl propionate or at least two.
7. a kind of preparation method of aluminum honeycomb energy storage device electrolyte described in any one of claims 1-6, which is characterized in that packet
Include following steps:
Lithium salts, organic solvent and additive are uniformly mixed, aluminum honeycomb energy storage device electrolyte is obtained.
8. the preparation method of aluminum honeycomb energy storage device electrolyte according to claim 7, which is characterized in that including following step
It is rapid:
Cyclic annular esters solvent and line style esters solvent are mixed in proportion, obtain solvent after adding additive mixing；Then plus
0-15 DEG C of addition lithium salts of temperature is kept after entering the drying of lithium type molecular sieve, obtains aluminum honeycomb energy storage device electrolyte.
9. a kind of aluminum honeycomb energy storage device, which is characterized in that including aluminum honeycomb energy storage device described in any one of claims 1-6
Electrolyte made from the preparation method of electrolyte or the described in any item aluminum honeycomb energy storage device electrolyte of claim 7-8.
10. a kind of preparation method of aluminum honeycomb energy storage device as claimed in claim 9, which comprises the following steps:
Cathode, diaphragm, anode and the aluminum honeycomb energy storage device electrolyte are assembled, aluminum honeycomb energy storage device is obtained.
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