CN108666640A - A kind of low temperature chemical synthesizing method of nickelic ternary lithium battery - Google Patents
A kind of low temperature chemical synthesizing method of nickelic ternary lithium battery Download PDFInfo
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- CN108666640A CN108666640A CN201810346542.2A CN201810346542A CN108666640A CN 108666640 A CN108666640 A CN 108666640A CN 201810346542 A CN201810346542 A CN 201810346542A CN 108666640 A CN108666640 A CN 108666640A
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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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
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Abstract
The present invention relates to a kind of nickelic ternary lithium battery processing methods of low temperature chemical conversion, belong to technical field of lithium batteries.Include the following steps：A, by propene carbonate cryocoagulation, the propene carbonate of solidification is added in the electrolyte A being made of electrolyte lithium salt and solvent acetic acid methyl esters, electrolyte B is obtained；B, nickelic ternary lithium battery to be injected is vacuumized, propene carbonate in electrolyte B is kept to solidify, by electrolyte B injection batteries, the battery of fluid injection is obtained after standing；C, by the electric current constant-current charge of 0.2 times of size of battery pool capacity magnitude to 3.5V, then with the electric current constant-current charge of 0.5 times of size of battery capacity value to 4V；Battery temperature is finally risen into room temperature, is sealed after standing, the nickelic ternary lithium battery of low temperature chemical conversion is obtained.The present invention makes total intercalated material have no chance to contact with electrode before not forming passivating film by the method that low temperature is melted into, it is prevented to be total to intercalated graphite electrode with lithium ion.
Description
Technical field
The present invention relates to a kind of low temperature chemical synthesizing methods of nickelic ternary lithium battery, belong to technical field of lithium batteries.
Background technology
The content that ternary material improves nickel can greatly promote the specific capacity of material, therefore nickelic ternary material is necessarily in the future
A kind of ideal material of large-sized battery.But with the raising of nickel content, six problems are caused：One, the Ni of positive electrode
Increase so that battery performance declines：Two, redox peaks polarization increases, and electrode is made to lead to volume from H2 to the transformation of H3 structures
It shrinks, capacity attenuation, cycle performance is deteriorated；Three, with the carry out discharge voltage reduction of cycle, Ni contents, which increase internal resistance, also increasing
The trend added；Four, heat decomposition temperature reduces, and thermal discharge increases, i.e., material thermal stability is deteriorated；Five, Ni4+Content is high, Ni4+Have
Very strong reduction inclination, is easy to happen Ni4+—Ni3+Reaction, to oxidation electrolyte so that thermal stability is deteriorated；Six, it deposits
In the Ni of large scale2+, it is in oxidisability to lead to material, and then electrode material can slowly decomposed liq electrolyte, battery be swollen
Gas, the safety problems such as to overcharge more prominent.
Electrode not only influences cycle performance by the destruction of total intercalation, also has a significant impact to thermostabilization.Carbonic acid third in electrolyte
Enester is total to intercalation before passivating film is formed with lithium ion, destroys Graphene electrodes.Existing method is that fluoro ethylene carbonate is added
Ester is pre-formed passivating film before total intercalation, but the fluorinated ethylene carbonate preparation process that the method uses is more complex, cost
It is higher, it limits it and is widely used.For this purpose, a kind of intercalation altogether that solves of searching becomes without adding the technique of other substances
The hot spot of research.
Application No. is 201310308133 Chinese invention patent disclose a kind of nickelic tertiary cathode material system lithium from
The high-voltage electrolyte of sub- battery.The invention discloses a kind of high-pressure electrolysis of nickelic tertiary cathode material system lithium ion battery
Liquid, the high-voltage electrolyte is by organic solvent, electrolyte lithium salt, positive film for additive, cathode film formation additive and anti-oxidant
Additive forms, wherein positive film for additive is methane-disulfonic acid methylene ester, and cathode film formation additive is fluoro ethylene carbonate
Ester, antioxidant is triethylene glycol methyl ether borate, on the basis of the gross mass of high-voltage electrolyte, positive film for additive
Additive amount be 0.5 ~ 1%；The additive amount of cathode film formation additive is 2 ~ 5%, and the additive amount of antioxidant is 0.5 ~ 1%.This
The high-voltage electrolyte of invention has preferable resistance to oxidation, high temperature resistant and security feature, ensures that battery has preferable cycle life；
There is higher conductivity simultaneously, can guarantee the high magnification and power characteristic of battery, also there is higher safety, can carry significantly
The security performance of high power battery.
Application No. is 201610653856 Chinese patents, disclose a kind of nickelic ternary lithium ion power battery electrolyte
And nickelic ternary lithium-ion-power cell.The invention discloses a kind of nickelic ternary lithium ion power battery electrolyte and nickelic three
First lithium-ion-power cell.The electrolyte includes non-aqueous organic solvent, lithium salts, conductive additive, film for additive and infiltration
Additive, wherein conductive additive are difluorophosphate, and film for additive is sulfuric acid vinyl ester, and infiltration additive is fluoro phosphonitrile
At least one of with fluorinated ethylene carbonate；By the synergistic effect of three of the above additive, mutually promote, it can be in electrode surface
Excellent SEI films are formed, and effectively facilitate each dynamic process of inside lithium ion cell.The power battery electrolyte tool of the present invention
There are good lithium ion transport properties and resistance to oxidation characteristic, ensure that the high power characteristic of power battery and good cyclicity
Can, while also there is higher safety.
Application No. is 201610786362 patents of invention to provide a kind of anti-overcharge electricity based on ternary lithium ion battery
Solve liquid and lithium ion battery.The present invention provides a kind of Overcharge prevention electrolyte and lithium-ion electric based on ternary lithium ion battery
Pond, it is characterised in that：The electrolyte includes lithium salts, organic solvent, overcharging additive, additive salt and functional additive；
The overcharging additive includes the aromatic derivant A and/or B of one or more, and the quality of derivative A, B respectively account for electrolysis
The 0.01% of liquid quality and 5%.Overcharge prevention electrolyte provided by the invention can be obviously improved nickel-cobalt-manganese ternary material, especially
The over-charging of the battery in the case where nickel content improves, and can improve overcharge under the premise of, reduced to the greatest extent and added
Add agent usage amount (<5%), charge/discharge capacity is had not significant impact, battery DCR is substantially unchanged, and cycle life is not bright
It is aobvious to reduce.
In conclusion the prior art prevents Graphene electrodes to be destroyed, mainly uses to solve the problems, such as total intercalation
Functional form additive is added in electrolyte（Predominantly fluorinated ethylene carbonate）Method, or in negative material be added at
Film additive fluorinated ethylene carbonate, these methods solve the problems, such as total intercalation to a certain extent, but additive draws
Enter and will produce certain influence to the performance of battery, and further make process complications, is unfavorable for extensive use.
Invention content
It is total to the problem of intercalation destroys graphite electrode for existing nickelic ternary lithium battery electrolytes.The present invention proposes a kind of solution
Certainly it is total to lithium battery processing method of the intercalation without adding other substances.
The present invention provides a kind of low temperature chemical synthesizing method of nickelic ternary lithium battery, which is characterized in that includes the following steps：
A, by propene carbonate cryocoagulation, by the propene carbonate addition freezing of solidification by electrolyte lithium salt and solvent second
In the electrolyte A of sour methyl esters composition, electrolyte B is obtained；
B, nickelic ternary lithium battery to be injected is vacuumized, keeps propene carbonate in electrolyte B to solidify, electrolyte B is noted
Enter in battery, the battery of fluid injection is obtained after standing；
C, it keeps propene carbonate in electrolyte B to solidify, open formation is carried out to the battery of fluid injection：By battery pool capacity magnitude
The electric current constant-current charge of 0.2 times of size is to 3.5V, then with the electric current constant-current charge of 0.5 times of size of battery capacity value to 4V；It will be electric
Pond temperature rises to room temperature, is sealed after standing, obtains the nickelic ternary lithium battery of low temperature chemical conversion.
Propene carbonate（Molecular formula：C4H6O3）For a kind of flammable liquid of no color or smell.With ether, acetone, benzene, chloroform,
Vinyl acetate etc. dissolves each other, and is dissolved in water and carbon tetrachloride.Very strong to the absorbability of carbon dioxide, property is stablized.Industrially take
Propylene oxide and carbon dioxide addition under a certain pressure, then vacuum distillation are made.Can be used for oil-based solvent, spin solvent,
The dispersant etc. of alkene, aromatic hydrocarbons extraction agent, carbon-dioxide absorbent, water-soluble dye and pigment.It can make high energy in electronics industry
The excellent medium of battery and capacitor.
Positive electrode is raw material the most key in lithium battery, and it is close that positive electrode mainly influences lithium ion battery energy
The performances such as degree, safety, cycle life.Since proportion may be up to 40% to anode material for lithium-ion batteries in battery cost
Left and right, so its cost also directly determines the height of battery cost.Lithium ion battery is there are many technology path, wherein mainstream
Technology path includes cobalt acid lithium (LCO), LiMn2O4 (LMO), cobalt nickel lithium manganate ternary material (NCM), nickel cobalt lithium aluminate ternary material
Expect (NCA) and LiFePO4 (LFP).Ternary material combines the advantages of positive electrodes such as cobalt acid lithium, lithium nickelate and LiMn2O4, simultaneous
Have that energy density is high, cycle life is longer, safety is preferable, advantage of lower cost is to high voltage good tolerability, high gram volume,
And the advantages such as cobalt content is few, it is most to be hopeful to replace cobalt acid lithium in electronic product, and mix with LiMn2O4 in power
The novel anode material of application.In ternary material, there is the nickelic ternary material development prospect of significant advantage most in energy density
It is wide.A large amount of result of study shows that cladding or doping treatment can improve the chemical property of positive electrode.Therefore, it is
Improve nickelic ternary material battery high-temperature storage performance, surface cladding processing can be carried out to it, reduces electrode/electrolyte interface
Side reaction occurs, and stabilizing material surface texture inhibits the dissolution of transition metal element, to reduce transition metal in the heavy of cathode
Product reduction and the destruction to cathode SEI reduce consumption of the SEI reparations to positive-active lithium ion；It can also be by stably-doped
The layer structure of nickelic positive electrode inhibits the transformation in storing process to spinelle and rock salt phase to a certain extent, to
Reduce the generation of material non-electroactive component in storage.
The lithium salts used in commodity lithium ion battery is LiPF at present6And LiBF4。LiBF4Electrolytic conductivity is not high, battery
Heavy-current discharge characteristic it is bad.LiPF6Facile hydrolysis, and thermal stability is bad, is connect with the moisture of air or the residual water of solvent
When touching, HF can be formed immediately, to have detrimental effect to the performance of battery;Meanwhile LiPF6Usually and ethylene carbonate
(EC) it shares and is made into electrolyte, effective SEI films could be formed in cathode, but the fusing point of EC is higher, which has limited the low of battery
Warm performance, therefore a large amount of research starts the synthesis and application that are dedicated to new lithium salts at present, it is desirable to performance can be found
The superior novel substance that can replace existing lithium salts, to improve the performance of lithium ion battery.The new lithium salts studied now,
The volume of anion is all very big, and the charge delocalization in anion is very strong, and this unique structure makes these salt have
There are very high conductivity, wide electrochemical window and high stability.Research is concentrated mainly on three classes lithium salts：Perfluoroalkyl sulphur
Acid imide lithium salts, novel lithium-borate complexes, novel phosphoric acid lithium-complex.Anion is all in the structure of aryl boric acid lithium
Containing big conjugatedπbond, charge height delocalization, this design feature improves its thermal stability, while also improving conductivity
And oxidation stability.
Methyl acetate（methyl acetate）Be increasingly becoming a kind of product of maturation in the world, for instead of acetone,
Butanone, ethyl acetate, pentamethylene etc..The Eastman company in the U.S. just replaced acetone solvent at 2005 with methyl acetate, because
For methyl acetate it is not belonging to the organic contamination emission that uses of limitation, it is new that coating, ink, resin, adhesive producing works can be reached
Environmental protection standard.
Lithium ion battery is because the advantages that having light weight, and long lifespan higher than energy, is used widely, low temperature lithium battery
Be it is a kind of used using made of special material and technique, being suitable for subzero cold environment, and discharge capacity and working performance
Show it is outstanding, generally require -40 degree left and right environment under work normally, discharge capacity is maintained at 80% or more, minimum work temperature
Degree can reach -50 DEG C.Low temperature lithium battery select VGCF and specific surface area (activated carbon of 2000 ± 500) ㎡/g be additive and
Its positive and negative pole material to match, the extraordinary electrolyte of injection addition special additive, ensure that the low temperature discharge work(of lithium battery
Can, while 70 DEG C of high temperature shelves volume change Shuai≤0.5% for 24 hours, has the safety and store function of conventional lithium battery.
The chemical conversion of lithium ion battery exactly carries out the lithium ion battery manufactured the charging of first time low current, it
Purpose be and the electrolyte liquid interface in electrode solids boundary, between two-phase is practised physiognomy, form a passivation layer, i.e. solid
Matter interface（SEI films）, organic matter in electrolyte, lithium ion can form solvation macromolecular therewith, if not having SEI films, lithium ion
The solvation macromolecular of formation, this macromolecular is bigger than lithium ion shape, can be embedded in Carbon anode layer, frequently embedded or abjection,
It easilys lead to carbon-coating to collapse, battery capacity reduces.And the formation of SEI films, the entrance of macromolecular can be prevented, only allow lithium ion into
Enter or the lithium ion in solvation macromolecular is allowed to separate, in embedded carbon layering.Therefore, the performance of the change battery pair of battery
It is most important.
Preferably：In step a, the temperature for freezing propene carbonate is -90 ~ -50 DEG C, and the additive amount of propene carbonate is electricity
Solve the 10 ~ 40% of liquid A gross masses.It is furthermore preferred that propene carbonate additive amount is the 30% of electrolyte A heavy amounts.
Preferably：In step a, electrolyte A is refrigerated to -90 ~ -50 DEG C in advance.
Preferably：In step a, electrolyte A includes following components in percentage by weight：Electrolyte lithium salt 10 ~ 15%, acetic acid
Methyl esters 85 ~ 90% is more selected as electrolyte lithium salt 10%, methyl acetate 90% to reach better effect.
Preferably：In step a, electrolyte lithium salt is by double-catechol-lithium borate（LBBB）With two-salicylic acids-lithium borate
（LBSB）Composition, and the molar ratio between the two is 80 ~ 60:20 ~ 40, preferred lithium salts proportioning is double-catechol-boric acid
Lithium（LBBB）With two-salicylic acids-lithium borate（LBSB）Molar ratio=70:30.
Preferably：In step b or c, it is -85 ~ -55 DEG C to keep the temperature that propene carbonate solidifies in electrolyte B.
Preferably：In step b, a length of 10 ~ 30 minutes when vacuumizing, in order to ensure the gas in pole piece gap is removed,
It is quickly infiltrated conducive to electrolyte, shortens time of repose, more preferably vacuumize 30 minutes.
Preferably：In step b, time of repose is 5 ~ 10 minutes, in order to ensure electrolyte complete wetting electrode, more preferably
10 minutes.
Preferably：In step c, time of repose is 10 minutes.
Compared with prior art, the present invention has advantageous effect below：
1, make total intercalated material have no chance to contact with electrode before not forming passivating film by the method that low temperature is melted into, prevent
Only it is total to intercalated graphite electrode with lithium ion.
2, this method does not have the introducing of additive, simple and practicable, is suitable for industrial production.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
A kind of low temperature chemical synthesizing method of nickelic ternary lithium battery of embodiment 1
It prepares according to the following steps：
A, by propene carbonate at -60 DEG C cryocoagulation, the propene carbonate of solidification is added to the electrolyte A of -70 DEG C of freezings
In, electrolyte A includes following components in percentage by weight：Electrolyte lithium salt 10%, solvent acetic acid methyl esters 90%, the electrolyte
Lithium salts is by double-catechol-lithium borate（LBBB）With two-salicylic acids-lithium borate（LBSB）Composition, and the molar ratio between the two is
80:20, the additive amount of propene carbonate is the 10% of electrolyte A gross masses, is electrolysed after electrolyte A addition propene carbonates
Liquid B,；
B, nickelic ternary lithium battery to be injected is vacuumized, a length of 10 minutes when vacuumizing, it is -60 to keep electrolyte temperature
DEG C, propene carbonate is curdled appearance in electrolyte B at this time, and by electrolyte B injection batteries, standing obtains fluid injection after five minutes
Nickelic ternary lithium battery；
C, it is -60 DEG C to keep electrolyte temperature, and propene carbonate is curdled appearance at this time, and opening is carried out to the battery of fluid injection
At：By the electric current constant-current charge of 0.2 times of size of battery pool capacity magnitude to 3.5V, then with 0.5 times of size of battery capacity value
Electric current constant-current charge is to 4V；Battery temperature is finally risen into room temperature, standing is sealed after ten minutes, obtains nickelic the three of low temperature chemical conversion
First lithium battery.
A kind of low temperature chemical synthesizing method of nickelic ternary lithium battery of embodiment 2
It prepares according to the following steps：
A, by propene carbonate at -65 DEG C cryocoagulation, the propene carbonate of solidification is added to the electrolyte A of -70 DEG C of freezings
In, electrolyte A includes following components in percentage by weight：Electrolyte lithium salt 11%, solvent acetic acid methyl esters 89%, the electrolyte
Lithium salts is by double-catechol-lithium borate（LBBB）With two-salicylic acids-lithium borate（LBSB）Composition, and the molar ratio between the two is
75:25, the additive amount of propene carbonate is the 15% of electrolyte A gross masses, is electrolysed after electrolyte A addition propene carbonates
Liquid B,；
B, nickelic ternary lithium battery to be injected is vacuumized, a length of 10 minutes when vacuumizing, it is -65 to keep electrolyte temperature
DEG C, propene carbonate is curdled appearance in electrolyte B at this time, and by electrolyte B injection batteries, standing obtains fluid injection after five minutes
Nickelic ternary lithium battery；
C, it is -65 DEG C to keep electrolyte temperature, and propene carbonate is curdled appearance at this time, and opening is carried out to the battery of fluid injection
At：By the electric current constant-current charge of 0.2 times of size of battery pool capacity magnitude to 3.5V, then with 0.5 times of size of battery capacity value
Electric current constant-current charge is to 4V；Battery temperature is finally risen into room temperature, standing is sealed after ten minutes, obtains nickelic the three of low temperature chemical conversion
First lithium battery.
A kind of low temperature chemical synthesizing method of nickelic ternary lithium battery of embodiment 3
It prepares according to the following steps：
A, by propene carbonate at -70 DEG C cryocoagulation, the propene carbonate of solidification is added to the electrolyte A of -70 DEG C of freezings
In, electrolyte A includes following components in percentage by weight：Electrolyte lithium salt 12%, solvent acetic acid methyl esters 88%, the electrolyte
Lithium salts is by double-catechol-lithium borate（LBBB）With two-salicylic acids-lithium borate（LBSB）Composition, and the molar ratio between the two is
70:30, the additive amount of propene carbonate is the 20% of electrolyte A gross masses, is electrolysed after electrolyte A addition propene carbonates
Liquid B,；
B, nickelic ternary lithium battery to be injected is vacuumized, a length of 15 minutes when vacuumizing, it is -70 to keep electrolyte temperature
DEG C, propene carbonate is curdled appearance in electrolyte B at this time, and by electrolyte B injection batteries, fluid injection is obtained after standing 8 minutes
Nickelic ternary lithium battery；
C, it is -70 DEG C to keep electrolyte temperature, and propene carbonate is curdled appearance at this time, and opening is carried out to the battery of fluid injection
At：By the electric current constant-current charge of 0.2 times of size of battery pool capacity magnitude to 3.5V, then with 0.5 times of size of battery capacity value
Electric current constant-current charge is to 4V；Battery temperature is finally risen into room temperature, standing is sealed after ten minutes, obtains nickelic the three of low temperature chemical conversion
First lithium battery.
A kind of low temperature chemical synthesizing method of nickelic ternary lithium battery of embodiment 4
It prepares according to the following steps：
A, by propene carbonate at -75 DEG C cryocoagulation, the propene carbonate of solidification is added to the electrolyte A of -75 DEG C of freezings
In, electrolyte A includes following components in percentage by weight：Electrolyte lithium salt 13%, solvent acetic acid methyl esters 87%, the electrolyte
Lithium salts is by double-catechol-lithium borate（LBBB）With two-salicylic acids-lithium borate（LBSB）Composition, and the molar ratio between the two is
65:35, the additive amount of propene carbonate is the 25% of electrolyte A gross masses, is electrolysed after electrolyte A addition propene carbonates
Liquid B,；
B, nickelic ternary lithium battery to be injected is vacuumized, a length of 30 minutes when vacuumizing, it is -60 to keep electrolyte temperature
DEG C, propene carbonate is curdled appearance in electrolyte B at this time, and by electrolyte B injection batteries, standing obtains fluid injection after ten minutes
Nickelic ternary lithium battery；
C, it is -60 DEG C to keep electrolyte temperature, and propene carbonate is curdled appearance at this time, and opening is carried out to the battery of fluid injection
At：By the electric current constant-current charge of 0.2 times of size of battery pool capacity magnitude to 3.5V, then with 0.5 times of size of battery capacity value
Electric current constant-current charge is to 4V；Battery temperature is finally risen into room temperature, standing is sealed after ten minutes, obtains nickelic the three of low temperature chemical conversion
First lithium battery.
A kind of low temperature chemical synthesizing method of nickelic ternary lithium battery of embodiment 5
It prepares according to the following steps：
A, by propene carbonate at -80 DEG C cryocoagulation, the propene carbonate of solidification is added to the electrolyte A of -80 DEG C of freezings
In, electrolyte A includes following components in percentage by weight：Electrolyte lithium salt 14%, solvent acetic acid methyl esters 86%, the electrolyte
Lithium salts is by double-catechol-lithium borate（LBBB）With two-salicylic acids-lithium borate（LBSB）Composition, and the molar ratio between the two is
60:40, the additive amount of propene carbonate is the 30% of electrolyte A gross masses, is electrolysed after electrolyte A addition propene carbonates
Liquid B,；
B, nickelic ternary lithium battery to be injected is vacuumized, a length of 20 minutes when vacuumizing, it is -75 to keep electrolyte temperature
DEG C, propene carbonate is curdled appearance in electrolyte B at this time, and by electrolyte B injection batteries, standing obtains fluid injection after five minutes
Nickelic ternary lithium battery；
C, it is -75 DEG C to keep electrolyte temperature, and propene carbonate is curdled appearance at this time, and opening is carried out to the battery of fluid injection
At：By the electric current constant-current charge of 0.2 times of size of battery pool capacity magnitude to 3.5V, then with 0.5 times of size of battery capacity value
Electric current constant-current charge is to 4V；Battery temperature is finally risen into room temperature, is sealed after standing 8 minutes, nickelic the three of low temperature chemical conversion are obtained
First lithium battery.
A kind of low temperature chemical synthesizing method of nickelic ternary lithium battery of embodiment 6
It prepares according to the following steps：
A, by propene carbonate at -85 DEG C cryocoagulation, the propene carbonate of solidification is added to the electrolyte A of -80 DEG C of freezings
In, electrolyte A includes following components in percentage by weight：Electrolyte lithium salt 15%, solvent acetic acid methyl esters 85%, the electrolyte
Lithium salts is by double-catechol-lithium borate（LBBB）With two-salicylic acids-lithium borate（LBSB）Composition, and the molar ratio between the two is
75:25, the additive amount of propene carbonate is the 40% of electrolyte A gross masses, is electrolysed after electrolyte A addition propene carbonates
Liquid B,；
B, nickelic ternary lithium battery to be injected is vacuumized, a length of 30 minutes when vacuumizing, it is -80 to keep electrolyte temperature
DEG C, propene carbonate is curdled appearance in electrolyte B at this time, and by electrolyte B injection batteries, standing obtains fluid injection after five minutes
Nickelic ternary lithium battery；
C, it is -80 DEG C to keep electrolyte temperature, and propene carbonate is curdled appearance at this time, and opening is carried out to the battery of fluid injection
At：By the electric current constant-current charge of 0.2 times of size of battery pool capacity magnitude to 3.5V, then with 0.5 times of size of battery capacity value
Electric current constant-current charge is to 4V；Battery temperature is finally risen into room temperature, standing is sealed after ten minutes, obtains nickelic the three of low temperature chemical conversion
First lithium battery.
A kind of low temperature chemical synthesizing method of nickelic ternary lithium battery of comparative example 1
It prepares according to the following steps：
A, by propene carbonate at -85 DEG C cryocoagulation, the propene carbonate of solidification is added to the electrolyte A of -45 DEG C of freezings
In, electrolyte A includes following components in percentage by weight：Electrolyte lithium salt 15%, solvent acetic acid methyl esters 85%, the electrolyte
Lithium salts is by double-catechol-lithium borate（LBBB）With two-salicylic acids-lithium borate（LBSB）Composition, and the molar ratio between the two is
75:25, the additive amount of propene carbonate is the 40% of electrolyte A gross masses, is electrolysed after electrolyte A addition propene carbonates
Liquid B,；
B, nickelic ternary lithium battery to be injected is vacuumized, a length of 30 minutes when vacuumizing, it is -45 to keep electrolyte temperature
DEG C, propene carbonate is semi-solid state in electrolyte B at this time, and by electrolyte B injection batteries, standing is noted after five minutes
The nickelic ternary lithium battery of liquid；
C, it is -45 DEG C to keep electrolyte temperature, and propene carbonate is semisolid shape at this time, and opening is carried out to the battery of fluid injection
At：By the electric current constant-current charge of 0.2 times of size of battery pool capacity magnitude to 3.5V, then with 0.5 times of size of battery capacity value
Electric current constant-current charge is to 4V；Battery temperature is finally risen into room temperature, standing is sealed after ten minutes, obtains nickelic the three of low temperature chemical conversion
First lithium battery.
For comparative example 1 during low temperature is melted into, propene carbonate is semisolid shape, is not solidified completely.
A kind of room temperature chemical synthesizing method of nickelic ternary lithium battery of comparative example 2
It prepares according to the following steps：
A, propene carbonate is added in electrolyte A, electrolyte A includes following components in percentage by weight：Electrolyte lithium salt
15%, solvent acetic acid methyl esters 85%, the electrolyte lithium salt is by double-catechol-lithium borate（LBBB）With two-salicylic acids-boric acid
Lithium（LBSB）Composition, and the molar ratio between the two is 75:25, the additive amount of propene carbonate is the 40% of electrolyte A gross masses,
Electrolyte B is obtained after electrolyte A addition propene carbonates,；
B, nickelic ternary lithium battery to be injected is vacuumized, a length of 30 minutes when vacuumizing, it is normal to keep electrolyte temperature
Temperature stands the nickelic ternary lithium battery for obtaining fluid injection after five minutes by electrolyte B injection batteries；
C, open formation is carried out to the battery of fluid injection：The electric current constant-current charge of 0.2 times of size of battery pool capacity magnitude is arrived
3.5V, then with the electric current constant-current charge of 0.5 times of size of battery capacity value to 4V；, it stands and seals after ten minutes, the height being melted into
Nickel ternary lithium battery.
The method that comparative example 2 is melted into using room temperature.
Test example
Nickelic ternary lithium battery prepared by Examples 1 to 6, comparative example 1~2, battery are same batch 811 types to be changed
Nickle cobalt lithium manganate battery；In normal temperature environment（25℃）And low temperature environment（-10℃）Middle progress capacitance loop test, test side
Method：The discharge capacity for the first time of test battery after 1C constant-current charges to 4.2V then to turn constant-voltage charge first, until electric current 0.05C,
Then 3V is discharged to 1C, and repeats 500 cycles, tested discharge capacity at this time, and calculate the capacity retention ratio of battery, tie
Fruit is as shown in table 1.
Table 1
| Example is not | Capacity retention ratio/- 10 DEG C after 500 cycles（%） | Capacity retention ratio/25 DEG C after 500 cycles（%） |
| Embodiment 1 | 84.76 | 85.11 |
| Embodiment 2 | 85.98 | 86.02 |
| Embodiment 3 | 85.41 | 85.76 |
| Embodiment 4 | 84.24 | 84.99 |
| Embodiment 5 | 88.21 | 88.74 |
| Embodiment 6 | 86.53 | 87.21 |
| Comparative example 1 | 75.52 | 76.50 |
| Comparative example 2 | 53.98 | 60.75 |
By test, propene carbonate is solidified completely and be melted into than half solidification chemical conversion with more stability, compared to normal
Temperature chemical conversion, cyclical stability, which has, to be obviously improved.
Claims (9)
1. a kind of low temperature chemical synthesizing method of nickelic ternary lithium battery, which is characterized in that include the following steps：
A, by propene carbonate cryocoagulation, by the propene carbonate addition freezing of solidification by electrolyte lithium salt and solvent second
In the electrolyte A of sour methyl esters composition, electrolyte B is obtained；
B, nickelic ternary lithium battery to be injected is vacuumized, keeps propene carbonate in electrolyte B to solidify, electrolyte B is noted
Enter in battery, the battery of fluid injection is obtained after standing；
C, it keeps propene carbonate in electrolyte B to solidify, open formation is carried out to the battery of fluid injection：By battery pool capacity magnitude
The electric current constant-current charge of 0.2 times of size is to 3.5V, then with the electric current constant-current charge of 0.5 times of size of battery capacity value to 4V；Finally
Battery temperature is risen into room temperature, is sealed after standing, the nickelic ternary lithium battery of low temperature chemical conversion is obtained.
2. a kind of low temperature chemical synthesizing method of nickelic ternary lithium battery according to claim 1, it is characterised in that：The step
In a, the temperature for freezing propene carbonate is -90 ~ -50 DEG C, the additive amount of propene carbonate be electrolyte A gross masses 10 ~
40%。
3. a kind of low temperature chemical synthesizing method of nickelic ternary lithium battery according to claim 1, it is characterised in that：The step
In a, electrolyte A is refrigerated to -90 ~ -50 DEG C in advance.
4. a kind of low temperature chemical synthesizing method of nickelic ternary lithium battery according to claim 1, which is characterized in that the step
In a, electrolyte A includes following components in percentage by weight：Electrolyte lithium salt 10 ~ 15%, methyl acetate 85 ~ 90%.
5. a kind of low temperature chemical synthesizing method of nickelic ternary lithium battery according to claim 1, it is characterised in that：The step
In a, electrolyte lithium salt is by double-catechol-lithium borate（LBBB）With two-salicylic acids-lithium borate（LBSB）Composition, and between the two
Molar ratio be 80 ~ 60:20~40.
6. a kind of low temperature chemical synthesizing method of nickelic ternary lithium battery according to claim 1, it is characterised in that：The step
In b or c, it is -85 ~ -55 DEG C to keep the temperature that propene carbonate solidifies in electrolyte B.
7. a kind of low temperature chemical synthesizing method of nickelic ternary lithium battery according to claim 1, it is characterised in that：The step
In b, a length of 10 ~ 30 minutes when vacuumizing.
8. a kind of low temperature chemical synthesizing method of nickelic ternary lithium battery according to claim 1, it is characterised in that：The step
In b, time of repose is 5 ~ 10 minutes.
9. according to a kind of low temperature chemical synthesizing method of nickelic ternary lithium battery described in claim 1, it is characterised in that：The step c
In, time of repose is 10 minutes.
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