CN107994231A - Flame-retardant additive, cosolvent and lithium ion battery - Google Patents
Flame-retardant additive, cosolvent and lithium ion battery Download PDFInfo
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- CN107994231A CN107994231A CN201710949979.0A CN201710949979A CN107994231A CN 107994231 A CN107994231 A CN 107994231A CN 201710949979 A CN201710949979 A CN 201710949979A CN 107994231 A CN107994231 A CN 107994231A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to technical field of lithium ion, discloses a kind of flame-retardant additive, cosolvent and lithium ion battery.The flame-retardant additive includes organophosphorous fire retardant, organic compounds containing nitrogen and halo acid esters, and the mass ratio of the organophosphorous fire retardant, the organic compounds containing nitrogen and the halo acid esters is 1：(0.3‑1.8)：(0.3‑1.8).The flame-retardant additive of the present invention and the cosolvent containing the flame-retardant additive have excellent flame retardant efficiency, the lithium ion battery prepared using the cosolvent has good flame retardant effect, so as to improve the general safety performance of lithium ion battery, while the lithium ion battery has good cycle performance.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of flame-retardant additive, contain the flame-retardant additive
Cosolvent and using lithium ion battery of the cosolvent as electrolyte.
Background technology
Since nineteen ninety Japan Sony, company produced first piece of commercialized lithium ion battery, lithium ion battery is with it
Operating voltage is high, small, light weight, energy density height, memory-less effect, that pollution is small, self discharge is small, has extended cycle life etc. is excellent
Point opens the chapter of lithium ion battery high speed development.In recent years, lithium rechargeable battery is produced except applying in consumer electronics
Outside product field, be also widely used on electric automobile and energy storage, and be considered as solve automobile exhaust pollution, reduce fossil energy disappear
Consumption, the important means of construction of energy internet.
Lithium ion battery is a kind of high energy system, and containing organic compounds such as inflammable esters and polyolefin, it is pacified
Full property risk has become restricts main problem of the lithium ion battery in the field such as electric car, energy storage large-scale application at present.Make
Into lithium ion battery security it is bad the reason for it is very much：On the one hand, lithium ion battery uses organic solution, is overcharged when battery is in
Organic solvent easily produces irreversible oxygenolysis in positive electrode surface during state, with big while amount of heat is released
The generation of imflammable gas is measured, causes internal temperature of battery and pressure to steeply rise, so as to bring the danger of explosion, burning to battery
Danger.On the other hand, inside lithium ion cell itself is there are a series of potential exothermic reactions, when battery is in use because each
When kind reason causes inside and outside short circuit and causes internal temperature rise larger, easily trigger these exothermic reactions and cause thermal runaway.By
In now widely used electrolyte solvent system be low-flash organosilane ester, it is often adjoint in battery explosion
Violent burning, has aggravated the extent of injury of safety hazards.
Safety problem is the major obstacle that lithium ion battery is applied on electric automobile and energy storage, particularly with large-scale energy storage
For battery system, the energy of battery system is very high (up to number MW even tens MW), and concentrating the safety problem of the battery of placement is
It is extremely concerned.The catching fire of battery or even mainly related, the battery thermal runaway of high combustibility to liquid electrolyte of exploding
Afterwards it is caused it is on fire be all that flammable electrolyte first burns.Therefore the research and development for the safe electrolyte of lithium ion battery seem outstanding
For key.
At present, for lithium-ion battery electrolytes there are the problem of, technical research mainly from research new additive agent enter
Hand, by the combination of variety classes, different content additive, improves the performance of battery.Therefore, it can be said that electrolyte technology is main
It is additive technology.But it there is no the additive technology specially developed for lithium-ion energy storage battery application at present, this allows for working as
Preceding additive technology is difficult to meet stored energy application demand, is mainly reflected in：(1) for the dedicated electrolyte research and development of energy-storage battery not
Foot, external lithium-ion battery electrolytes company, such as Mitsubishi, the research of long-term absorbed lithium-ion battery electrolytes, its pin
To the lithium ion battery of specific model, the exploitation of all targeted electrolyte prescription, multifunction additive is chosen from solvent
Exploitation has further investigation, to realize the optimization of battery performance.The research for focusing on functional additive of electrolyte research,
At present, the related patents of lithium-ion battery electrolytes additive rest in Japanese human hand more.But even electrolyte skill
The leading Japan of art, also has no energy-storage battery special electrolysis liquid.The country is still few for the research for storing up usable lithium ion battery,
Lack the matching correct of the lithium ion battery material system for energy storage system, to grinding for the electrolyte of energy storage lithium ion battery
Study carefully also seldom.(2) electrolyte anti-flammability solve it is undesirable, current electrolyte system uses carbonic ester more, as DMC, DEC,
EMC, EC, PC etc.；In addition also have carboxylic acid ester compound and ether compound, these organic matters be all it is flammable, especially
Some compound high volatilities, flash-point and burning point are low, if battery improper use, easily ignite these organic solvents, burns
Even explode.
To solve the above problems, need to improve to existing electrolyte system, improve its anti-flammability so that improve lithium from
The security of sub- battery.
The content of the invention
The purpose of the invention is to overcome the above-mentioned problems in the prior art, there is provided a kind of flame-retardant additive, contain
There is the cosolvent of the flame-retardant additive and using lithium ion battery of the cosolvent as electrolyte.The flame-retardant additive of the present invention
There is excellent flame retardant efficiency with the cosolvent containing the flame-retardant additive, the lithium ion battery prepared using the cosolvent is had
Good flame retardant effect, so that the general safety performance of lithium ion battery is improved, while the lithium ion battery has well
Cycle performance.
To achieve these goals, in a first aspect, the present invention provides a kind of flame-retardant additive, the flame-retardant additive bag
Include organophosphorous fire retardant, organic compounds containing nitrogen and halo acid esters, the organophosphorous fire retardant, the organic compounds containing nitrogen and
The mass ratio of the halo acid esters is 1：(0.3-1.8)：(0.3-1.8).
Second aspect, the present invention provides a kind of cosolvent, which includes lithium salts, organic solvent and fire-retardant addition
Agent, the flame-retardant additive are flame-retardant additive of the present invention.
The third aspect, the present invention provides a kind of lithium ion battery, which includes cathode, anode, membrane, outer
Shell and electrolyte, the electrolyte are cosolvent of the present invention.
The flame-retardant additive and cosolvent (for a kind of fire-retardant cosolvent) of the present invention, preparation process are simple and with excellent
Flame retardant efficiency, fundamentally reduces the hydroperoxyl radical [H] in traditional electrolyte liquid system, using the cosolvent prepare lithium from
Sub- battery has good flame retardant effect, so that the general safety performance of lithium ion battery is improved, while the lithium ion battery
With good cycle performance, meet requirement of the application such as energy storage to lithium ion battery.
Specifically, using lithium ion battery made of the cosolvent when heated, organophosphorous fire retardant can gasify decomposition, release
The fire-retardant free radical [P] with hydroperoxyl radical [H] ability in capture electrolyte system is released, prevents hydrocarbon combustion
Or the chain reaction of explosion occurs, so as to improve the thermal runaway temperature of lithium ion battery, increases the high temperature safety of battery；It is nitrogenous
The mechanism of action of organic compound is similar with organophosphorous fire retardant, when it is heated, resolves into gaseous state nitride, then decomposes and releases
[N] free radical put combines to form NH with hydroperoxyl radical3Deng incombustible, and then prevent the progress of chain reaction；Halo
Acid esters is flash-point is very high or organic solvent without flash-point, and after substituting hydrogen atom such as fluorine atom, the hydrogen content of solvent molecule reduces, can
Combustion property reduces, and is added to the heat endurance that electrolyte can be obviously improved in electrolyte, meanwhile, by the sucting electronic effect of F elements,
Optimize solid electrolyte interface film, improve the compatibility between electrolyte and active material, and then the chemical property of stabilized electrodes,
So that lithium ion battery keeps good cycle performance.When organophosphorous fire retardant, organic compounds containing nitrogen and halo acid esters are with spy
When fixed ratio mixes, obtained lithium ion battery can be caused to have good flame retardant effect and cycle performance concurrently.
A kind of preferred embodiment according to the present invention, the cosolvent include lithium salts, organic solvent, flame-retardant additive and
SEI film film for additive, foregoing four classes material can easily, it is complete mutually molten altogether, and formed it is stable be suitable for lithium from
The non-aqueous solution for possessing flame retarding function of sub- battery, thus obtained lithium ion battery have obvious excellent flame retardant effect and follow
Ring performance.
Embodiment
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of flame-retardant additive, the flame-retardant additive includes organophosphorous fire retardant, contains
Nitrogen organic compound and halo acid esters, the matter of the organophosphorous fire retardant, the organic compounds containing nitrogen and the halo acid esters
Amount is than being 1：(0.3-1.8)：(0.3-1.8).
In order to further improve the flame retardant effect of flame-retardant additive and cosolvent containing the flame-retardant additive so that be made
Lithium ion battery have good flame retardant effect and cycle performance concurrently, it is the organophosphorous fire retardant, described nitrogenous under preferable case
The mass ratio of organic compound and the halo acid esters is 1：(0.5-1.2)：(0.5-1.2).
Under preferable case, organophosphorous fire retardant is organophosphorus ester, it is further preferred that the organophosphorus ester is phosphoric acid
Trimethyl (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), triphenyl phosphate (TPP), di(2-ethylhexyl)phosphate benzene toluene ester
(CDP) and at least one of diphenyl octyl phosphate (DPOF).
Under preferable case, organic compounds containing nitrogen is amides compound and/or isocyanate ester compound, further excellent
Selection of land, the amides compound at least one of for dimethylacetylamide (DMAC), diethyl acetamide and benzamide,
The isocyanate ester compound is different for Triallyl isocyanurate (also known as triallyl cyanurate, TAC), triallyl
At least one of cyanate (TAIC) and toluene di-isocyanate(TDI).
Under preferable case, halo acid esters is halogenated phosphate and/or halocarbonate, wherein, the halogen in halo acid esters
It is preferably F, it is further preferred that the halogenated phosphate is (2,2,2- trifluoroethyl) diethylphosphate for F or Cl or Br
(TDP), three-(2,2,2- trifluoroethyls) phosphite esters (TTFP) and two-(2,2,2- trifluoroethyls)-methyl phosphorodithioates (BMP)
At least one of, the halocarbonate is chlorocarbonic acid vinyl acetate, fluorinated ethylene carbonate and three fluoropropylene carbonates
At least one of (TFPC).
Wherein, the present inventor under study for action it has furthermore been found that compared with other combination for, when flame-retardant additive is phosphorus
During the mixture of sour trimethyl, dimethylacetylamide and (2,2,2- trifluoroethyl) diethylphosphate, it can further improve
The flame retardant effect of flame-retardant additive and cosolvent containing the flame-retardant additive so that obtained lithium ion battery has concurrently preferably
Flame retardant effect and cycle performance.
Second aspect, the present invention provides a kind of cosolvent, which includes lithium salts, organic solvent and fire-retardant addition
Agent, the flame-retardant additive are above-mentioned flame-retardant additive.
Under preferable case, on the basis of the weight of the cosolvent, the content of the flame-retardant additive is 1-50 weight %.
In order to further improve the flame retardant effect of cosolvent so that obtained lithium ion battery has good flame retardant effect and cyclicity concurrently
Can, it is further preferred that on the basis of the weight of the cosolvent, the content of the flame-retardant additive is 10-40 weight %, more
More preferably 20-40 weight %.
In order to further improve the cycle performance of obtained lithium ion battery, it is preferable that the cosolvent further includes solid electricity
Matter interfacial film film for additive (SEI films film for additive) is solved, it is further preferred that the SEI films film for additive is enester
Class compound, it is further preferred that the alkene ester type compound is vinylene carbonate (VC), vinyl acetate (VA), Asia
At least one of sulfuric acid vinyl ester (ES) and propylene sulfite (PS).
Under preferable case, on the basis of the weight of the cosolvent, the content of the SEI films film for additive is
0.01%-1 weight %, more preferably 0.05%-0.5 weight %.
In the cosolvent of the present invention, for lithium salts, there is no particular limitation, can be various lithium salts commonly used in the art, excellent
In the case of choosing, lithium salts LiF, Li2O、Li2O2、LiPF6、LiBF4、LiBF3Cl、LiClO4, dioxalic acid lithium borate (LiBOB), two
Fluorine Lithium bis (oxalate) borate (LiDFOB), LiAsF6、LiSbF6、LiCF3SO3、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN
(SO2C4F9)2、LiC(SO2CF3)3、LiPF3(C3F7)3、LiB(CF3)4And LiBF3C2F5At least one of.Wherein, lithium salts exists
Concentration in the cosolvent can be 0.3-2.8mol/L, be preferably 0.7-2.2mol/L.
In the cosolvent of the present invention, for organic solvent, there is no particular limitation, can be commonly used in the art various to have
Solvent, under preferable case, organic solvent R1COOR2、R3OCOOR4And R5CH2OCH2R6At least one of, R1-R6Each
It independently is alkane, alkane halide, alkene, alkene halides, phenyl ring or phenyl ring halides, R1-R6Carbon number it is each only
It is on the spot 1-10.Wherein, alkane halide, alkene halides, phenyl ring halides can be respectively alkane, alkene, on phenyl ring
At least one protium is substituted by least one halogens, and halogens can be F, Cl, Br.
Wherein it is preferred to the organic solvent is ethylene carbonate (EC), diethyl carbonate (DEC), methyl ethyl carbonate
(EMC), at least one of n,N-Dimethylformamide (DMF), ethyl butyrate (EB) and ethyl propionate (EP), such as can be
EC and DEC is according to 1:The mixed liquor of 1 mass ratio mixing.
In the cosolvent of the present invention, for the amount of organic solvent, there is no particular limitation, is meeting lithium salts, flame-retardant additive
And in the case of the amount of SEI films film for additive (or can also include other materials), remaining amount is organic solvent
Amount.
In the cosolvent of the present invention, for the preparation method of cosolvent, there is no particular limitation, if by each component according to
Foregoing content is uniformly mixed, and can be various methods commonly used in the art, specific mixed method is those skilled in the art
Known, details are not described herein.
The third aspect, the present invention provides a kind of lithium ion battery, which includes cathode, anode, membrane, outer
Shell and electrolyte, the electrolyte are the above-mentioned cosolvent of the present invention.
In the lithium ion battery of the present invention, for cathode, there is no particular limitation, can be it is commonly used in the art it is various just
Pole, wherein positive electrode can be LiCoO2、LiNixCoyAlzO2、LiNixMnyCozO2、LiMnPO4And LiCoPO4In at least
One kind, 0≤x, y, z≤1, x+y+z=1.The composition and preparation method of specific cathode are well known to those skilled in the art,
This is repeated no more.
In the lithium ion battery of the present invention, for anode, there is no particular limitation, can be commonly used in the art various negative
Pole, wherein negative material can be Delanium, native graphite, carbonaceous mesophase spherules (MCMB), Si and its alloy, Sn and its conjunction
Gold, lithium metal and its alloy, LixMyOzAnd Li4Ti5-xMxO12At least one of, wherein LixMyOzIn M for Ti, V, Cr,
Fe, Co, Ni, Cu, Zn, Ge or Sn, the value of x, y, z meet the requirement for forming chemical molecular formula, Li4Ti5-xMxO12In M be
Mg, Al, Ba, Sr or Ta, 0≤x≤1.The composition and preparation method of specific anode are well known to those skilled in the art, herein
Repeat no more.
In the lithium ion battery of the present invention, for membrane, there is no particular limitation, can be it is commonly used in the art it is various every
Film, its septation can be at least one of polyethylene (PE), polypropylene (PP) and ceramic compound.
In the lithium ion battery of the present invention, for shell, there is no particular limitation, can be commonly used in the art various outer
Shell, wherein shell can be at least one in plastic-aluminum packaging film, resin material, engineering plastics, aluminum and aluminum alloy mateial and steel
Kind, wherein plastic-aluminum packaging film can arrange for nylon layer, adhesive, intermediate layer aluminium foil, adhesive, hot sealing layer according to certain order
The multilayer film of composition.It is foregoing to be commercially available.
The lithium ion battery of the present invention can also include lug, and for lug, there is no particular limitation, can be this area
Common various lugs, wherein lug can be in copper and its alloy, aluminium and its alloy, nickel and its alloys and silver and its alloy
The electric conductor of at least one definite shape being prepared.
In the present invention, for the preparation method of lithium ion battery, there is no particular limitation, can be commonly used in the art each
Kind method, this is well known to those skilled in the art, and details are not described herein.
Embodiment
The present invention will be described in detail by way of examples below, but is not intended to limit the present invention.Following embodiments
In, unless otherwise instructed, method used is the conventional method of this area, and reagent used can be commercially available.
The atmosphere requirements of argon gas atmosphere glove box：Water content ＜ 3ppm, oxygen content ＜ 3ppm.
Embodiment 1
The present embodiment is used for the cosolvent for illustrating the present invention.
(1) reference electrolyte is prepared in argon gas atmosphere glove box：By lithium salts LiPF6It is uniformly mixed, makees with organic solvent
On the basis of electrolyte, wherein, organic solvent is the mixed liquor of EC and DEC, and the mass ratio of EC and DEC are 1：1, lithium salts LiPF6's
Concentration is 1mol/L.
(2) reference electrolyte and flame-retardant additive are uniformly mixed in argon gas atmosphere glove box, stand 4h, then add
SEI film film for additive vinylene carbonates, stir evenly, obtain 1kg cosolvent.Wherein, flame-retardant additive is tripotassium phosphate
The mixture of ester, dimethylacetylamide and (2,2,2- trifluoroethyl) diethylphosphate, trimethyl phosphate, dimethylacetamide
Amine, the mass ratio of (2,2,2- trifluoroethyls) diethylphosphate are 1：0.8：0.8, using the weight of gained 1kg cosolvent as base
Standard, the content of the flame-retardant additive is 30 weight %, and the content of vinylene carbonate is 0.1 weight %, reference electrolyte
Content is 69.9 weight %.
Embodiment 2
The present embodiment is used for the cosolvent for illustrating the present invention.
(1) reference electrolyte is prepared in argon gas atmosphere glove box：By lithium salts LiPF6It is uniformly mixed, makees with organic solvent
On the basis of electrolyte, wherein, organic solvent is the mixed liquor of EC and DEC, and the mass ratio of EC and DEC are 1：1, lithium salts LiPF6's
Concentration is 1.5mol/L.
(2) reference electrolyte and flame-retardant additive are uniformly mixed in argon gas atmosphere glove box, stand 4h, then add
SEI film film for additive vinyl acetates, stir evenly, obtain 1kg cosolvent.Wherein, flame-retardant additive is phosphoric acid hexichol first
The mixture of phenyl ester, triallyl isocyanate and three-(2,2,2- trifluoroethyl) phosphite esters, di(2-ethylhexyl)phosphate benzene toluene ester, three
The mass ratio of allyl iso cyanurate and three-(2,2,2- trifluoroethyls) phosphite esters is 1：0.5：0.5, it is molten altogether with gained 1kg
On the basis of the weight of agent, the content of the flame-retardant additive is 40 weight %, and the content of vinyl acetate is 0.5 weight %, base
The content of quasi- electrolyte is 59.5 weight %.
Embodiment 3
The present embodiment is used for the cosolvent for illustrating the present invention.
(1) reference electrolyte is prepared in argon gas atmosphere glove box：By lithium salts LiPF6It is uniformly mixed, makees with organic solvent
On the basis of electrolyte, wherein, organic solvent is the mixed liquor of EC and DEC, and the mass ratio of EC and DEC are 1：1, lithium salts LiPF6's
Concentration is 1.2mol/L.
(2) reference electrolyte and flame-retardant additive are uniformly mixed in argon gas atmosphere glove box, stand 4h, then add
SEI film film for additive ethylene sulfites, stir evenly, obtain 1kg cosolvent.Wherein, flame-retardant additive is pungent for diphenyl
The mixture of base phosphate, Triallyl isocyanurate and chlorocarbonic acid vinyl acetate, diphenyl octyl phosphate, triallyl
Isocyanuric acid ester and the mass ratio of chlorocarbonic acid vinyl acetate are 1：1.2：1.2, on the basis of the weight of gained 1kg cosolvent, institute
The content for stating flame-retardant additive is 20 weight %, and the content of ethylene sulfite is 0.05 weight %, the content of reference electrolyte
For 79.95 weight %.
Embodiment 4
The present embodiment is used for the cosolvent for illustrating the present invention.
(1) reference electrolyte is prepared in argon gas atmosphere glove box：By lithium salts LiPF6It is uniformly mixed, makees with organic solvent
On the basis of electrolyte, wherein, organic solvent is the mixed liquor of EC and DEC, and the mass ratio of EC and DEC are 1：1, lithium salts LiPF6's
Concentration is 1mol/L.
(2) reference electrolyte and flame-retardant additive are uniformly mixed in argon gas atmosphere glove box, stand 4h, then add
SEI film film for additive propylene sulfites, stir evenly, obtain 1kg cosolvent.Wherein, flame-retardant additive is phosphoric acid triphen
The mixture of ester, benzamide and three fluoropropylene carbonates, triphenyl phosphate, benzamide and three fluoropropylene carbonates
Mass ratio is 1：1：1, on the basis of the weight of gained 1kg cosolvent, the content of the flame-retardant additive is 35 weight %, sulfurous
The content of acid propylene ester is 0.8 weight %, and the content of reference electrolyte is 64.2 weight %.
Embodiment 5
According to the method for embodiment 1, the difference is that, trimethyl phosphate, dimethylacetylamide, (2,2,2- trifluoroethyl) two
The mass ratio of ethyl phosphonic acid ester is 1：0.3：0.3.
Embodiment 6
According to the method for embodiment 1, the difference is that, trimethyl phosphate, dimethylacetylamide, (2,2,2- trifluoroethyl) two
The mass ratio of ethyl phosphonic acid ester is 1：1.8：1.8.
Embodiment 7
According to the method for embodiment 1, the difference is that, SEI film film for additive is not contained in cosolvent.
Specifically, step (2) is：Reference electrolyte and flame-retardant additive are uniformly mixed in argon gas atmosphere glove box,
4h is stood, obtains 1kg cosolvent.Wherein, flame-retardant additive is trimethyl phosphate, dimethylacetylamide and (2,2,2- trifluoro second
Base) diethylphosphate mixture, trimethyl phosphate, dimethylacetylamide, (2,2,2- trifluoroethyl) diethylphosphate
Mass ratio be 1：0.8：0.8, on the basis of the weight of gained 1kg cosolvent, the content of the flame-retardant additive is 30 weights
% is measured, the content of reference electrolyte is 70 weight %.
Embodiment 8
According to the method for embodiment 1, the difference is that, flame-retardant additive is replaced with into tributyl phosphate, toluene diisocynate
The mixture of ester and two-(2,2,2- trifluoroethyl)-methyl phosphorodithioates, tributyl phosphate, toluene di-isocyanate(TDI) and two-(2,
2,2- trifluoroethyls)-methyl phosphorodithioate mass ratio be 1：0.8：0.8.
Comparative example 1
According to the method for embodiment 1, the difference is that, using reference electrolyte as cosolvent.
Comparative example 2
According to the method for embodiment 1, the difference is that, flame-retardant additive does not include organophosphorous fire retardant.
Specifically, step (2) is：Reference electrolyte and flame-retardant additive are uniformly mixed in argon gas atmosphere glove box,
4h is stood, SEI film film for additive vinylene carbonates is then added, stirs evenly, obtain 1kg cosolvent.Wherein, it is fire-retardant to add
Add mixture of the agent for dimethylacetylamide and (2,2,2- trifluoroethyl) diethylphosphate, dimethylacetylamide with (2,2,
2- trifluoroethyls) diethylphosphate mass ratio be 0.8：0.8, it is described fire-retardant on the basis of the weight of gained 1kg cosolvent
The content of additive is 30 weight %, and the content of vinylene carbonate is 0.1 weight %, and the content of reference electrolyte is 69.9 weights
Measure %.
Comparative example 3
According to the method for embodiment 1, the difference is that, flame-retardant additive does not include organic compounds containing nitrogen.
Specifically, step (2) is：Reference electrolyte and flame-retardant additive are uniformly mixed in argon gas atmosphere glove box,
4h is stood, SEI film film for additive vinylene carbonates is then added, stirs evenly, obtain 1kg cosolvent.Wherein, it is fire-retardant to add
Add agent for trimethyl phosphate and the mixture of (2,2,2- trifluoroethyl) diethylphosphate, trimethyl phosphate and (2,2,2- tri-
Fluoro ethyl) diethylphosphate mass ratio be 1：0.8, on the basis of the weight of gained 1kg cosolvent, the flame-retardant additive
Content be 30 weight %, the content of vinylene carbonate is 0.1 weight %, and the content of reference electrolyte is 69.9 weight %.
Comparative example 4
According to the method for embodiment 1, the difference is that, flame-retardant additive does not include halo acid esters.
Specifically, step (2) is：Reference electrolyte and flame-retardant additive are uniformly mixed in argon gas atmosphere glove box,
4h is stood, SEI film film for additive vinylene carbonates is then added, stirs evenly, obtain 1kg cosolvent.Wherein, it is fire-retardant to add
Add agent for trimethyl phosphate and the mixture of dimethylacetylamide, the mass ratio of trimethyl phosphate and dimethylacetylamide is 1：
0.8, on the basis of the weight of gained 1kg cosolvent, the content of the flame-retardant additive is 30 weight %, vinylene carbonate
Content is 0.1 weight %, and the content of reference electrolyte is 69.9 weight %.
Comparative example 5
According to the method for embodiment 1, the difference is that, trimethyl phosphate, dimethylacetylamide, (2,2,2- trifluoroethyl) two
The mass ratio of ethyl phosphonic acid ester is 1：0.1：0.1.
Comparative example 6
According to the method for embodiment 1, the difference is that, trimethyl phosphate, dimethylacetylamide, (2,2,2- trifluoroethyl) two
The mass ratio of ethyl phosphonic acid ester is 1：2.2：2.2.
Test example
(1) flame self-gravitation time (SET) and flame retarding efficiency：Take embodiment 1-8, comparative example 1- respectively in glove box
6 cosolvent sample drop is on glass fibre cotton balls (diameter 1cm).Glass fibre cotton balls is lighted in fume hood, when record burns
Between.Every kind of system measures 5 Duplicate Samples, is averaged, as a result such as table 1.Wherein, the flame self-gravitation time refers to the electricity of unit mass
Solve liquid to burn the required time, be the flammable evaluation method of common lithium-ion battery electrolytes, calculation formula is：SET
=t/m, t are the quality of electrolyte to be measured from starting to light to burning end required time, m for electrolyte.
Table 1
| The flame self-gravitation time (s/g) | Flame retarding efficiency (%) | |
| Embodiment 1 | 2.51 | 96.7 |
| Embodiment 2 | 0.22 | 99.7 |
| Embodiment 3 | 6.84 | 90.9 |
| Embodiment 4 | 1.16 | 98.5 |
| Embodiment 5 | 8.55 | 88.6 |
| Embodiment 6 | 8.95 | 88.1 |
| Embodiment 7 | 2.89 | 96.2 |
| Embodiment 8 | 6.73 | 91.0 |
| Comparative example 1 | 75.08 | 0 |
| Comparative example 2 | 48.15 | 35.9 |
| Comparative example 3 | 39.58 | 47.3 |
| Comparative example 4 | 32.36 | 56.9 |
| Comparative example 5 | 22.68 | 69.8 |
| Comparative example 6 | 26.44 | 64.8 |
From the data of table 1, cosolvent of the invention has the fire resistance and security performance significantly improved, wherein,
The 75.08s/g of flame self-gravitation time from reference electrolyte (being not added with flame-retardant additive) is reduced to fire-retardant cosolvent
0.22s/g, flame retarding efficiency be up to 99.7% (wherein, when continuing to improve the content of flame-retardant additive, flame self-gravitation time meeting
Further reduce, flame retarding efficiency can further improve).
(2) electrical conductivity：Embodiment 1-8, contrast are measured using plum Teller-support benefit SevenEasy type electric conductivities instrument respectively
The cosolvent of example 1-6 is in -20 DEG C, 0 DEG C, 20 DEG C, 40 DEG C, 60 DEG C, 80 DEG C of electrical conductivity (mS/cm), as a result respectively such as the institute of table 2
Show.
Table 2
From the data of table 2, cosolvent of the invention (when especially flame-retardant additive content is 20-35 weight %) tool
There is excellent electrical conductivity, hence it is evident that higher than the electrical conductivity for the reference electrolyte for being not added with flame-retardant additive.
(3) lithium ion battery is prepared：Make using nickle cobalt lithium manganate NCM111 types ternary material as positive electrode, with lithium titanate
For negative material, respectively using embodiment 1-8, comparative example 1-6 cosolvent as electrolyte, using PP-PE composite diaphragms as every
Film, using plastic-aluminum packaging film as shell, using copper nickel plating as positive pole ear, using aluminium as negative lug, using lamination assembler
Skill prepares 6Ah lithium ion batteries.
Measure the thermal runaway temperature and temperature rise rate of each lithium ion battery：Using special accelerating calorimeter (the resistance to ARC254 that speeds)
The result of each lithium ion battery progress thermal runaway detection to being prepared, thermal runaway temperature and temperature rise rate is shown in Table 3 respectively.
Table 3
| Thermal runaway temperature (DEG C) | Temperature rise rate (DEG C/min) | |
| Embodiment 1 | 266.38 | 1.05 |
| Embodiment 2 | 279.01 | 1.01 |
| Embodiment 3 | 249.45 | 1.11 |
| Embodiment 4 | 272.97 | 1.03 |
| Embodiment 5 | 244.13 | 1.12 |
| Embodiment 6 | 243.98 | 1.12 |
| Embodiment 7 | 262.96 | 1.06 |
| Embodiment 8 | 251.86 | 1.10 |
| Comparative example 1 | 210.09 | 1.19 |
| Comparative example 2 | 216.23 | 1.17 |
| Comparative example 3 | 219.47 | 1.16 |
| Comparative example 4 | 224.26 | 1.15 |
| Comparative example 5 | 232.03 | 1.13 |
| Comparative example 6 | 229.48 | 1.14 |
From the data of table 3, cosolvent of the invention can improve the initial heat generating spot of lithium ion battery, reduce heat and lose
Temperature rise rate during control, so as to be obviously improved the security of lithium ion battery.
(4) cycle performance of lithium ion battery：Using the cycle performance of discharge and recharge instrument measure lithium ion battery, wherein, survey
Fixed condition includes：At 23 DEG C, each lithium ion battery is charged into 2.8V with 1C (6A) electric current respectively, after voltage rises to 2.8V with
Constant-potential charge, limitation voltage are 2.9V, cut-off current 0.6A, are shelved 10 minutes；Battery with 1C current discharges to 1.5V,
Shelve 10 minutes.Above step n times are repeated, 1C current discharges record battery and exist to the capacity of 1.5V after obtaining the circulation of battery n times
23 DEG C of discharge capacity first, and by capacity retention ratio before and after following formula calculating circulation.
The discharge capacity * 100% of capacity retention ratio=n-th cyclic discharge capacity/first, the results are shown in Table 4.
Table 4
| Discharge capacity (Ah) first | Cycle-index | Capacity retention ratio (%) after circulation | |
| Embodiment 1 | 6.13 | 4200 | 99.3 |
| Embodiment 2 | 6.14 | 4200 | 96.5 |
| Embodiment 3 | 6.13 | 4200 | 97.5 |
| Embodiment 4 | 6.13 | 4200 | 98.1 |
| Embodiment 5 | 6.12 | 4000 | 94.5 |
| Embodiment 6 | 6.13 | 4000 | 94.2 |
| Embodiment 7 | 6.14 | 3800 | 80.5 |
| Embodiment 8 | 6.13 | 3800 | 87.4 |
| Comparative example 1 | 6.12 | 3300 | 77.2 |
| Comparative example 2 | 6.14 | 3800 | 85.5 |
| Comparative example 3 | 6.13 | 3800 | 84.6 |
| Comparative example 4 | 6.12 | 3800 | 83.3 |
| Comparative example 5 | 6.13 | 3800 | 88.8 |
| Comparative example 6 | 6.14 | 3800 | 89.4 |
From the data of table 4, the lithium ion battery being prepared by the cosolvent of the present invention, which has, substantially preferably to follow
Ring performance.
From upper each result, the security that cosolvent of the invention can be obviously improved lithium ion battery (greatly shortens
Flame self-gravitation time, the initial temperature for improving electrical conductivity, improving battery thermal runaway), and the lithium-ion electric being prepared by it
Pond has excellent cycle performance.
The preferred embodiment of the present invention described in detail above, still, the present invention is not limited thereto.In the skill of the present invention
In art concept, technical scheme can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, these simple variants and combination should equally be considered as content disclosed in this invention, belong to
Protection scope of the present invention.
Claims (10)
- A kind of 1. flame-retardant additive, it is characterised in that the flame-retardant additive include organophosphorous fire retardant, organic compounds containing nitrogen and Halo acid esters, the mass ratio of the organophosphorous fire retardant, the organic compounds containing nitrogen and the halo acid esters is 1：(0.3- 1.8)：(0.3-1.8).
- 2. flame-retardant additive according to claim 1, it is characterised in that the organophosphorous fire retardant, described nitrogenous organic The mass ratio of compound and the halo acid esters is 1：(0.5-1.2)：(0.5-1.2).
- 3. flame-retardant additive according to claim 1 or 2, it is characterised in that the organophosphorous fire retardant is organic phosphoric acid Ester；And/orThe organic compounds containing nitrogen is amides compound and/or isocyanate ester compound；And/orThe halo acid esters is halogenated phosphate and/or halocarbonate.
- 4. flame-retardant additive according to claim 3, it is characterised in that the organophosphorus ester is trimethyl phosphate, phosphorus At least one of triethylenetetraminehexaacetic acid ester, tributyl phosphate, triphenyl phosphate, di(2-ethylhexyl)phosphate benzene toluene ester and diphenyl octyl phosphate； And/orThe amides compound is at least one of dimethylacetylamide, diethyl acetamide and benzamide；And/orThe isocyanate ester compound is Triallyl isocyanurate, triallyl isocyanate and toluene di-isocyanate(TDI) At least one of；And/orThe halogenated phosphate is (2,2,2- trifluoroethyls) diethylphosphate, three-(2,2,2- trifluoroethyls) phosphite esters At least one of with two-(2,2,2- trifluoroethyls)-methyl phosphorodithioates；And/orThe halocarbonate is at least one in chlorocarbonic acid vinyl acetate, fluorinated ethylene carbonate and three fluoropropylene carbonates Kind.
- 5. a kind of cosolvent, it is characterised in that the cosolvent includes lithium salts, organic solvent and flame-retardant additive, described fire-retardant to add It is the flame-retardant additive in claim 1-4 described in any one to add agent.
- 6. cosolvent according to claim 5, it is characterised in that described fire-retardant on the basis of the weight of the cosolvent The content of additive is 1-50 weight %.
- 7. the cosolvent according to claim 5 or 6, it is characterised in that the cosolvent further includes solid electrolyte interface film Film for additive, the solid electrolyte interface film film for additive is vinylene carbonate, vinyl acetate, sulfurous acid ethene At least one of ester and propylene sulfite.
- 8. cosolvent according to claim 7, it is characterised in that on the basis of the weight of the cosolvent, the solid The content of electrolyte interface film film for additive is 0.01%-1 weight %.
- 9. the cosolvent according to claim 5 or 6, it is characterised in that the lithium salts is LiF, Li2O、Li2O2、LiPF6、 LiBF4、LiBF3Cl、LiClO4, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, LiAsF6、LiSbF6、LiCF3SO3、LiN (SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2C4F9)2、LiC(SO2CF3)3、LiPF3(C3F7)3、LiB(CF3)4And LiBF3C2F5 At least one of；And/orThe organic solvent is R1COOR2、R3OCOOR4And R5CH2OCH2R6At least one of, R1-R6It is each independently alkane Hydrocarbon, alkane halide, alkene, alkene halides, phenyl ring or phenyl ring halides, R1-R6Carbon number be each independently 1- 10。
- 10. a kind of lithium ion battery, which includes cathode, anode, membrane, shell and electrolyte, it is characterised in that The electrolyte is the cosolvent described in any one in claim 5-9.
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| CN112252025A (en) * | 2020-10-15 | 2021-01-22 | 西安工程大学 | Finishing method for improving flame retardant property of polyester-cotton fabric |
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