CN108428939A - A kind of nickelic ternary lithium battery electrolytes of stable circulation - Google Patents
A kind of nickelic ternary lithium battery electrolytes of stable circulation Download PDFInfo
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- 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
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
The invention belongs to technical fields prepared by ternary battery electrolyte, and in particular to a kind of nickelic ternary lithium battery electrolytes of stable circulation.The nickelic ternary lithium battery electrolytes of the present invention, its additive is the mixture of dimethylamino methyl phenyl ethers anisole, 4' amino Benzo-15-crown 5 ether and six stearate of sorbitol polyoxyethylene ether, electrolyte non-wetting phenomenon caused by six stearate of sorbitol polyoxyethylene ether can improve the blockings such as the rupture that battery cathode hole is generated by charge and discharge and catabolite, to improve the cycle performance of battery；The OCH of dimethylamino methyl phenyl ethers anisole3It is reacted with solvolyte and generates LiOCH3, form the SEI films of efficient stable；5 ether of 4' amino Benzo-15-crown can form packaging type chelate with lithium ion, can improve the solubility of lithium salts, realize zwitterion pair efficiently separate and the separation of lithium ion and solvent molecule；Three's collective effect improves the cycle performance of electrolyte.
Description
Technical field
The invention belongs to technical fields prepared by ternary battery electrolyte, and in particular to a kind of nickelic ternary lithium battery electrolysis
Liquid.
Background technology
Ternary material（Nickle cobalt lithium manganate）The specific capacity of material, therefore nickelic ternary material can be greatly promoted by improving the content of nickel
Expect a kind of ideal material of necessarily large-sized battery in future.
Cycle performance is particularly important to the performance of lithium ion battery；Longer cycle life means that less resource disappears
Consumption.Thus, the factor of cycle performance of lithium ion battery is influenced, is roughly divided into：1, material category, the selection of material be influence lithium from
The first element of sub- battery performance.The cycle performance of material is poor, on the one hand may be the changes in crystal structure in cyclic process
It is too fast to take off lithium to which embedding lithium continued to complete, on the one hand may be that densification can not be generated with corresponding electrolyte due to active material
Uniform SEI films cause active material that side reaction occurs to early with electrolyte and the too fast consumption of electrolyte is made to influence to recycle in turn.
2, positive and negative anodes are compacted：Positive and negative anodes compacting is excessively high, although the energy density of battery core can be improved, can also reduce to a certain extent
The cycle performance of material.It is analyzed from theory, compacting is bigger, and the structure destruction being equivalent to material is bigger, and the structure of material
It is the basis that ensures lithium ion battery and can recycle；In addition, positive and negative anodes, which are compacted higher battery core, is difficult to ensure higher guarantor
Liquid measure, and protect the basis that liquid measure is the cycle that battery core completes normal circulation or more time.3, moisture：Excessive moisture can with it is positive and negative
Pole active material occurs side reaction, destroys its structure and then influence to recycle, while excess moisture is also unfavorable for the formation of SEI films.
4, it is coated with film density：The baking water removal that thinner film density can increase the high rate performance of battery core, pole piece and naked battery core can also be held
Easily, error when too thin film density is coated with certainly may be more difficult to control, and bulky grain in active material may also can be to painting
Cloth, rolling adversely affect, and more numbers of plies mean more foils and diaphragm, and then mean higher cost and more
Low energy density.5, cathode is excessive：The reason of cathode excess considers the influence and coating of irreversible capacity for the first time in addition to needs
Except film density deviation, the influence to cycle performance is also one and considers.For cobalt acid lithium plus graphite system, cathode graphite
It is relatively conventional as " short slab " side in cyclic process.If cathode is excessively inadequate, battery core may not analyse lithium before cycle,
But the little but negative pole structure of anode structure variation is destroyed serious and can not receive positive offer completely after recycling hundreds of times
Lithium ion to analyse lithium, cause capacity to decline too early.6, electrolyte content：Electrolyte content deficiency, which has an impact cycle, mainly to be had
Three reasons, first, reservoir quantity is insufficient, although second is that reservoir quantity abundance ageing time is inadequate or positive and negative anodes are due to compacting
Immersion liquid caused by crossing the reasons such as high is insufficient, third, being finished as cycle battery core electrolyte inside is consumed.It is positive and negative to thirdly
The Microscopic of the pole especially matching of cathode and electrolyte is the formation of SEI that is fine and close and stablizing, both in cyclic process
The depletion rate of electrolyte.On the one hand incomplete SEI films can not effectively prevent cathode that side reaction occurs to disappear with electrolyte
Electrolyte is consumed, it is reversible to consume on the one hand to regenerate SEI films with the progress of cycle at the defective position of SEI films
Lithium source and electrolyte.7, the objective condition tested：Charge-discharge magnification, blanking voltage, charge cutoff electric current, survey in test process
The external worlds such as super-charge super-discharge in examination, test room temperature, the unexpected interruption in test process, contact internal resistance of the test point with battery core because
Element all can more or less influence cycle performance test result.
As wooden barrel principle, in the factor of many influence battery core cycle performances, final deciding factor is
Most short slab in factors.Meanwhile between these influence factors, also suffering from reciprocal effect.In same material and it is made
Under ability, higher cycle often means that lower energy density, finds the binding site for being just met for customer demand, as possible
Ensure consistency made of battery core, is only where most important task.
Chinese invention patent application number 201610193138.7 disclose electrolyte and comprising the electrolyte it is nickelic just
Pole lithium ion battery, the electrolyte include non-aqueous organic solvent, lithium salts and additive, and the additive includes cyclic sulfates
Close object and isocyanurate compound.Compared with prior art, there is excellent room temperature using the lithium ion battery of the electrolyte
Cycle performance, high temperature cyclic performance and high temperature storage service life, and the gas production during high temperature storage can be substantially reduced.
Chinese invention patent application number 201310547286.0 disclose a kind of high circulation stability, large capacity composite wood
Expect lithium battery and preparation method thereof.A kind of high circulation stability of the disclosure of the invention, the composite lithium battery of large capacity, including
Shell, positive plate, electrolyte, negative plate and diaphragm, the negative plate is by composite nanometer particle, acetylene black and Kynoar
Mixture is covered on copper foil and is made；The electrolyte is lithium perchlorate, lithium hexafluoro phosphate, lithium tetrafluoroborate solution；It is described just
Pole piece be lithium metal, cobalt acid lithium, LiMn2O4 or 811 type nickle cobalt lithium manganates one kind；The composite nanometer particle is by semiconductor material
Nano particle outer surface made of material is assembled with multilayer water-soluble ionic polymers and is made.The beneficial effects of the invention are as follows：This hair
Bright prepared composite lithium battery, the carbon-coating of self assembly have the entry/leave that enough gaps facilitate lithium ion, simultaneously
Carbon-coating is connected with semi-conducting material nano particle by polar bond, and cyclical stability is high, capacity is big.
Chinese invention patent application number 201110434737.0 discloses a kind of method preparing anode material of lithium battery, electricity
The preparation method of pond positive electrode is in lithium nickel cobalt manganese oxygen or using it in the precursor solution of the doping type oxide of matrix, to divide
Improver is not added, is carried out at low temperature by chemically reacting, prepares lithium nickel cobalt manganese oxygen or using it as the doping proximate matter of matrix
Then material calcines the anode that synthetic product is used for lithium battery.The preparation process of the present invention has suitable nargin, is easy to control, makes
Product reaches the other uniform mixing of molecular level, the energy consumption being minimized in preparation process.And it is electric for 3C electronic products are improved
Specific capacity, the stable circulation performance in pond, take into account the factors such as safety and environmental protection, are conducive to expand it in electronic product and energy field
Using.
Chinese invention patent application number 201410595659.6 disclose a kind of lithium ion battery high-voltage electrolyte and its
Purposes, the electrolyte include：Nonaqueous solvents, lithium salts, first kind additive and the second class additive；Wherein, the nonaqueous solvents
For carbonate-based solvent；Include fluoro alkene ether, chemical molecular formula CHF in the first kind additive2CF=CHOCFHCF3；It should
Second class additive is any one or two in 1,3- propene sultones, Isosorbide-5-Nitrae-butylene sultones, vinylene carbonate
Kind or more mixture.Lithium-ion electrolyte provided by the invention and nickel ion doped match materials, can meet lithium ion battery
Recycling under high voltage condition so that cyclical stability is excellent under high voltages for nickel ion doped battery.
But as the specific discharge capacity of the nickelic ternary material of increase of Ni contents increases to 220mAh g1 by 160mAhg1
More than, but its capacity retention ratio, thermal stability and high-temperature storage performance all decrease, and significantly limit its industrialization development
Using.The study found that the reason of causing these problems of nickelic ternary material is complicated, it is broadly divided into material itself and interface two and asks greatly
Topic.In recent years, exploitation also becomes an important research direction suitable for the electrolyte of nickelic ternary material.But at present
Until, the research direction about such material electrolyte is mainly to conventional LiPF6Base carbonates electrolyte is improved,
But these measures are very limited to the improvement result of nickelic tertiary cathode material cycle performance, cyclical stability is still paid no attention to
Think.It is very necessary to find a kind of electrolyte that can effectively improve cycle performance thus.
Invention content
The problem of for existing nickelic ternary system lithium battery poor circulation, the present invention propose a kind of height of stable circulation
Nickel ternary lithium battery electrolytes.
To solve the above problems, the present invention uses following technical scheme：
A kind of nickelic ternary lithium battery electrolytes of stable circulation, the electrolyte include the organic solvent of 20~40 parts by weight, 8~
The additive of the lithium salts of 22 parts by weight, 3~12 parts by weight；Wherein, the additive is dimethylamino methyl phenyl ethers anisole, 4'- amino
The mixture of phendioxin 5- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether.
Electrolyte is four big critical material of lithium ion battery（Anode, cathode, diaphragm, electrolyte）One of, it is known as lithium ion
" blood " of battery plays the role of conducting electronics in the battery between positive and negative anodes, is that lithium ion battery obtains high voltage, high ratio
The guarantee of the advantages that energy.Electrolyte generally by raw materials such as the organic solvent of high-purity, electrolyte lithium salt, necessary additives,
Under certain condition, it is formulated by a certain percentage.
Organic solvent is the main part of electrolyte, closely related with the performance of electrolyte, and organic solvent is using preceding necessary tight
Lattice control quality, such as require purity 99.9% or more, moisture must reach 10*l0 -6Below.The purity and stabilization of solvent
There are close ties between voltage, the oxidizing potential of purity organic solvent up to standard is in 5V or so, the oxidizing potential pair of organic solvent
Prevent over-charging of battery, safety from having great significance in research.Further, the nickelic ternary lithium battery of above-mentioned a kind of stable circulation
Electrolyte, wherein the solvent is glutaronitrile, adiponitrile, dicyandiamide, acetonitrile, malononitrile, p-chlorobenzyl cyanide, the chloro- 5- nitros of 2-
Benzonitrile, m-trifluoromethyl benzene acetonitrile, cyaniding benzyl, isophthalodinitrile, butyronitrile, acrylonitrile, dimethylaminopropionitrile, propionitrile, hydroxyl
At least one of acetonitrile.
Further, the nickelic ternary lithium battery electrolytes of above-mentioned a kind of stable circulation, wherein the organic solvent is penta
At least one of dintrile, adiponitrile, malononitrile, hydroxyacetonitrile.
Further, the nickelic ternary lithium battery electrolytes of above-mentioned a kind of stable circulation, wherein the lithium salts is double trifluoros
At least one of sulfonyl methane imine lithium, two (trimethyl fluoride sulfonyl) imine lithiums.
Further, the nickelic ternary lithium battery electrolytes of above-mentioned a kind of stable circulation, wherein the dimethylamino benzene
Methyl ether, 4'- amino benzos -15- hat 5- ethers and six stearate three's mass ratio of sorbitol polyoxyethylene ether are 3~6:2~9:5
~15.
Further, the nickelic ternary lithium battery electrolytes of above-mentioned a kind of stable circulation, wherein the dimethylamino benzene
Methyl ether, 4'- amino benzos -15- hat 5- ethers and six stearate three's mass ratio of sorbitol polyoxyethylene ether are 4~6:3~8:6
~12.
Further, the nickelic ternary lithium battery electrolytes of above-mentioned a kind of stable circulation, wherein the dimethylamino benzene
Methyl ether, 4'- amino benzos -15- hat 5- ethers and six stearate three's mass ratio of sorbitol polyoxyethylene ether are 5:5:8.
The present invention configures organic solvent, lithium salts, additive to form electrolyte in the form of compositions, various in composition
Additive interacts, and influences each other, improves the security performances such as the pressure-resistant performance of electrolyte, and conductivity will not be caused to reduce
The shortcomings of, the shortcomings that its surface-active can be utilized to reduce electrolysis fluid viscosity, avoid previous fire retardant, solve asking for compatibility
Topic.Meanwhile addition additive can reduce workload and reduce cost in the form of compositions.
A kind of nickelic ternary lithium battery electrolytes of stable circulation of the present invention have following beneficial compared with the prior art
Effect：
（1）Six stearate of sorbitol polyoxyethylene ether can improve the rupture and degradation that battery cathode hole is generated by charge and discharge
Electrolyte non-wetting phenomenon caused by the blockings such as product, to improve the cycle performance of battery；
（2）The OCH3 of dimethylamino methyl phenyl ethers anisole is reacted with solvolyte generates LiOCH3, form efficient stable
SEI films；
（3）4'- amino benzos -15- hat 5- ethers can form packaging type chelate with lithium ion, can improve the solubility of lithium salts,
Realize zwitterion pair efficiently separate and the separation of lithium ion and solvent molecule；
(4) dimethylamino methyl phenyl ethers anisole, 4'- amino benzos -15- hat 5- ethers and six stearate three of sorbitol polyoxyethylene ether
Person's collective effect improves the cycle performance of electrolyte.
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.
Embodiment 1
A kind of nickelic ternary lithium battery electrolytes of stable circulation, the electrolyte include 30 parts by weight organic solvent glutaronitrile,
Two (trimethyl fluoride sulfonyl) imine lithiums of 15 parts by weight, the additive of 8 parts by weight；The additive is dimethylamino benzene first
Ether, 4'- amino benzos -15- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether are 5 according to mass ratio:5:It is made after 8 mixing
It is standby to form.
The preparation method of the nickelic ternary lithium battery electrolytes of above-mentioned stable circulation, includes the following steps：Dimethylamino
Methyl phenyl ethers anisole, 4'- amino benzos -15- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether are 5 according to mass ratio:5:8 mixing
After compositions of additives is prepared；By organic solvent, lithium salts, additive agent mixture, it is sufficiently stirred, is electrolysed at 25 DEG C
Liquid.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 1 obtains, and is obtained
To simulated battery.
Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, the electrolyte prepared to embodiment 1
Conductivity test is carried out, obtains the results are shown in Table 1；Cycle performance of battery test is carried out to simulated battery obtained above, battery follows
Ring performance test conditions are：In 25 DEG C of environment, carries out constant current under the current value of 0.5C and the voltage of 4.2V and constant pressure is filled
Electricity to electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Embodiment 2
A kind of nickelic ternary lithium battery electrolytes of stable circulation, the electrolyte include 20 parts by weight organic solvent dicyandiamide,
Double trifluoromethanesulfonimide lithiums of 10 parts by weight, the additive of 4 parts by weight；The additive be dimethylamino methyl phenyl ethers anisole,
It is 4 that 4'- amino benzos -15-, which is preced with 5- ethers and six stearate of sorbitol polyoxyethylene ether according to mass ratio,:4:It is prepared after 9 mixing
It forms.
The preparation method of the nickelic ternary lithium battery electrolytes of above-mentioned stable circulation, includes the following steps：Dimethylamino
Methyl phenyl ethers anisole, 4'- amino benzos -15- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether are 4 according to mass ratio:4:9 mixing
After compositions of additives is prepared；By organic solvent, lithium salts, additive agent mixture, it is sufficiently stirred, is electrolysed at 25 DEG C
Liquid.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 2 obtains, and is obtained
To simulated battery.
Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, the electrolyte prepared to embodiment 2
Conductivity test is carried out, obtains the results are shown in Table 1；Cycle performance of battery test is carried out to simulated battery obtained above, battery follows
Ring performance test conditions are：In 25 DEG C of environment, carries out constant current under the current value of 0.5C and the voltage of 4.2V and constant pressure is filled
Electricity to electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Embodiment 3
A kind of nickelic ternary lithium battery electrolytes of stable circulation, which includes the organic solvent acetonitrile of 24 parts by weight, 12
Two (trimethyl fluoride sulfonyl) imine lithiums of parts by weight, the additive of 6 parts by weight；The additive is dimethylamino benzene first
Ether, 4'- amino benzos -15- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether are 4 according to mass ratio:5:After 12 mixing
It is prepared.
The preparation method of the nickelic ternary lithium battery electrolytes of above-mentioned stable circulation, includes the following steps：Dimethylamino
Methyl phenyl ethers anisole, 4'- amino benzos -15- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether are 4 according to mass ratio:5:12 is mixed
Compositions of additives is prepared after conjunction；By organic solvent, lithium salts, additive agent mixture, it is sufficiently stirred at 25 DEG C, obtains electricity
Solve liquid.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 3 obtains, and is obtained
To simulated battery.
Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, the electrolyte prepared to embodiment 3
Conductivity test is carried out, obtains the results are shown in Table 1；Cycle performance of battery test is carried out to simulated battery obtained above, battery follows
Ring performance test conditions are：In 25 DEG C of environment, carries out constant current under the current value of 0.5C and the voltage of 4.2V and constant pressure is filled
Electricity to electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Embodiment 4
A kind of nickelic ternary lithium battery electrolytes of stable circulation, the electrolyte include the organic solvent of 24 parts by weight to chlorobenzene second
The additive of nitrile, double trifluoromethanesulfonimide lithiums of 14 parts by weight, 7 parts by weight；The additive is dimethylamino benzene first
Ether, 4'- amino benzos -15- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether are 4 according to mass ratio:6:After 11 mixing
It is prepared.
The preparation method of the nickelic ternary lithium battery electrolytes of above-mentioned stable circulation, includes the following steps：Dimethylamino
Methyl phenyl ethers anisole, 4'- amino benzos -15- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether are 4 according to mass ratio:6:11 is mixed
Compositions of additives is prepared after conjunction；By organic solvent, lithium salts, additive agent mixture, it is sufficiently stirred at 25 DEG C, obtains electricity
Solve liquid.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 4 obtains, and is obtained
To simulated battery.
Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, the electrolyte prepared to embodiment 4
Conductivity test is carried out, obtains the results are shown in Table 1；Cycle performance of battery test is carried out to simulated battery obtained above, battery follows
Ring performance test conditions are：In 25 DEG C of environment, carries out constant current under the current value of 0.5C and the voltage of 4.2V and constant pressure is filled
Electricity to electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Embodiment 5
A kind of nickelic ternary lithium battery electrolytes of stable circulation, the electrolyte include 23 parts by weight organic solvent between fluoroform
The additive of base benzene acetonitrile, two (trimethyl fluoride sulfonyl) imine lithiums of 14 parts by weight, 5 parts by weight；The additive is diformazan
Base aminoanisole, 4'- amino benzos -15- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether are 5 according to mass ratio:
6:It is prepared after 11 mixing.
The preparation method of the nickelic ternary lithium battery electrolytes of above-mentioned stable circulation, includes the following steps：Dimethylamino
Methyl phenyl ethers anisole, 4'- amino benzos -15- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether are 5 according to mass ratio:6:11 is mixed
Compositions of additives is prepared after conjunction；By organic solvent, lithium salts, additive agent mixture, it is sufficiently stirred at 25 DEG C, obtains electricity
Solve liquid.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 5 obtains, and is obtained
To simulated battery.
Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, the electrolyte prepared to embodiment 5
Conductivity test is carried out, obtains the results are shown in Table 1；Cycle performance of battery test is carried out to simulated battery obtained above, battery follows
Ring performance test conditions are：In 25 DEG C of environment, carries out constant current under the current value of 0.5C and the voltage of 4.2V and constant pressure is filled
Electricity to electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Embodiment 6
A kind of nickelic ternary lithium battery electrolytes of stable circulation, the electrolyte include 23 parts by weight penta propionitrile of organic solvent,
Double trifluoromethanesulfonimide lithiums of 10 parts by weight, the additive of 6 parts by weight；The additive be dimethylamino methyl phenyl ethers anisole,
It is 5 that 4'- amino benzos -15-, which is preced with 5- ethers and six stearate of sorbitol polyoxyethylene ether according to mass ratio,:8:It is prepared after 12 mixing
It forms.
The preparation method of the nickelic ternary lithium battery electrolytes of above-mentioned stable circulation, includes the following steps：Dimethylamino
Methyl phenyl ethers anisole, 4'- amino benzos -15- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether are 5 according to mass ratio:8:12 is mixed
Compositions of additives is prepared after conjunction；By organic solvent, lithium salts, additive agent mixture, it is sufficiently stirred at 25 DEG C, obtains electricity
Solve liquid.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that embodiment 6 obtains, and is obtained
To simulated battery.
Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, the electrolyte prepared to embodiment 6
Conductivity test is carried out, obtains the results are shown in Table 1；Cycle performance of battery test is carried out to simulated battery obtained above, battery follows
Ring performance test conditions are：In 25 DEG C of environment, carries out constant current under the current value of 0.5C and the voltage of 4.2V and constant pressure is filled
Electricity to electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Comparative example 1
A kind of nickelic ternary lithium battery electrolytes of stable circulation, the electrolyte include 30 parts by weight organic solvent glutaronitrile,
Two (trimethyl fluoride sulfonyl) imine lithiums of 15 parts by weight, the additive of 8 parts by weight；The additive is dimethylamino benzene first
Ether.
The preparation method of the nickelic ternary lithium battery electrolytes of above-mentioned stable circulation, includes the following steps：By organic solvent,
Lithium salts, additive are sufficiently stirred at 25 DEG C, obtain electrolyte.
Aluminum-shell battery is selected, m in positive plate（811 type nickle cobalt lithium manganates）:m（Acetylene black）:m（Kynoar）=85:
7:8, artificial graphite is cathode, and Celgard2500 polypropylene micropore diaphragms, electrolyte is the electrolyte that comparative example 1 obtains, and is obtained
To simulated battery.
Desk-top conductivity measurement is tested under the conditions of 25 DEG C using Cond7400, the electrolyte prepared to comparative example 1
Conductivity test is carried out, obtains the results are shown in Table 1；Cycle performance of battery test is carried out to simulated battery obtained above, battery follows
Ring performance test conditions are：In 25 DEG C of environment, carries out constant current under the current value of 0.5C and the voltage of 4.2V and constant pressure is filled
Electricity to electric current be 0.1C, under 0.5C multiplying powers carry out constant-current discharge to 2.5V final voltage, carry out 100 times cycle charging and
Electric discharge, simulated battery rated capacity are 15mAh.By carrying out cycle performance of battery test to simulated battery, the results are shown in Table
1。
Table 1：
| Embodiment | Multiplying power discharging 3C/1C | Highest tolerable temperature（℃） | Conductivity（mS/cm） | Discharge specific volume for the first time（mAh/g） | Capacity retention ratio after recycling 100 times（%） |
| Embodiment 1 | 93% | 133 | 7.09 | 198 | 90% |
| Embodiment 2 | 91% | 132 | 7.01 | 210 | 88% |
| Embodiment 3 | 92% | 134 | 7.04 | 207 | 86% |
| Embodiment 4 | 89% | 134 | 7.06 | 206 | 89% |
| Embodiment 5 | 89% | 135 | 7.05 | 217 | 84% |
| Embodiment 6 | 92% | 134 | 7.03 | 200 | 86% |
| Comparative example 1 | 87% | 82 | 6.88 | 186 | 73% |
Claims (7)
1. a kind of nickelic ternary lithium battery electrolytes of stable circulation, which is characterized in that the electrolyte includes 20~40 parts by weight
Organic solvent, the lithium salts of 8~22 parts by weight, 3~12 parts by weight additive；Wherein, the additive is dimethylamino
The mixture of methyl phenyl ethers anisole, 4'- amino benzos -15- hat 5- ethers and six stearate of sorbitol polyoxyethylene ether.
2. the nickelic ternary lithium battery electrolytes of a kind of stable circulation according to claim 1, which is characterized in that described organic
Solvent is glutaronitrile, adiponitrile, dicyandiamide, acetonitrile, malononitrile, p-chlorobenzyl cyanide, the chloro- 5- nitrobenzonitriles of 2-, fluoroform
At least one in base benzene acetonitrile, cyaniding benzyl, isophthalodinitrile, butyronitrile, acrylonitrile, dimethylaminopropionitrile, propionitrile, hydroxyacetonitrile
Kind.
3. the nickelic ternary lithium battery electrolytes of a kind of stable circulation according to claim 4, which is characterized in that described organic
Solvent is at least one of glutaronitrile, adiponitrile, malononitrile, hydroxyacetonitrile.
4. the nickelic ternary lithium battery electrolytes of a kind of stable circulation according to claim 1, which is characterized in that the lithium salts
For at least one of double trifluoromethanesulfonimide lithiums, two (trimethyl fluoride sulfonyl) imine lithiums.
5. the nickelic ternary lithium battery electrolytes of a kind of stable circulation according to claim 1, which is characterized in that the diformazan
Base aminoanisole, 4'- amino benzos -15- hat 5- ethers and six stearate three's mass ratio of sorbitol polyoxyethylene ether be 3~
6:2~9:5~15.
6. the nickelic ternary lithium battery electrolytes of a kind of stable circulation according to claim 1, which is characterized in that the diformazan
Base aminoanisole, 4'- amino benzos -15- hat 5- ethers and six stearate three's mass ratio of sorbitol polyoxyethylene ether be 4~
6:3~8:6~12.
7. the nickelic ternary lithium battery electrolytes of a kind of stable circulation according to claim 1, which is characterized in that the diformazan
Base aminoanisole, 4'- amino benzos -15- hat 5- ethers and six stearate three's mass ratio of sorbitol polyoxyethylene ether are 5:
5:8。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111446499A (en) * | 2020-04-03 | 2020-07-24 | 江西理工大学 | Mixed lithium salt electrolyte |
| CN112771022A (en) * | 2018-10-04 | 2021-05-07 | 魁北克电力公司 | Additive for electrolytes in Li-ion batteries |
-
2018
- 2018-03-20 CN CN201810227125.6A patent/CN108428939A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112771022A (en) * | 2018-10-04 | 2021-05-07 | 魁北克电力公司 | Additive for electrolytes in Li-ion batteries |
| EP3860974A4 (en) * | 2018-10-04 | 2022-08-17 | Hydro-Québec | Additives for electrolytes in li-ion batteries |
| CN112771022B (en) * | 2018-10-04 | 2024-03-19 | 魁北克电力公司 | Additive for electrolytes in Li-ion batteries |
| CN111446499A (en) * | 2020-04-03 | 2020-07-24 | 江西理工大学 | Mixed lithium salt electrolyte |
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