CN107275671A - A kind of electrolyte and preparation method and lithium battery for suppressing Li dendrite - Google Patents
A kind of electrolyte and preparation method and lithium battery for suppressing Li dendrite Download PDFInfo
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- CN107275671A CN107275671A CN201710552057.6A CN201710552057A CN107275671A CN 107275671 A CN107275671 A CN 107275671A CN 201710552057 A CN201710552057 A CN 201710552057A CN 107275671 A CN107275671 A CN 107275671A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to technical field of lithium batteries, specifically related to a kind of electrolyte and preparation method and lithium battery for suppressing Li dendrite, affiliated electrolyte includes lithium salts, nanometer additive, dispersant, organic solvent, the concentration of the lithium salts is 0.5 10mol/L, and the mass fraction of the nanometer additive is 0.01%~10%.The nonaqueous electrolytic solution that the present invention is prepared using fluoride nano-particle as nanometer additive is so that battery has reached longer effect of more stable, safer, life-span.And the effect of the electrolyte of fluoride in the battery is a continual and steady process, contrasted with traditional film forming nanometer additive, fluoride nano particles can reach the effect of live fast filming in negative terminal surface, so as to effectively inhibit the growth of Li dendrite and the side reaction of positive electrode surface；Other fluoride nano particles can be stabilized in the electrolytic solution, the appearance for the problems such as being failed in the absence of effect.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to the electrolyte and preparation method and lithium of a kind of suppression Li dendrite
Battery.
Background technology
With the development of science and technology, the mankind are growing day by day to the demand of the energy, and commercialized lithium ion battery is due to theory
Specific capacity is relatively low can not to meet demand, and the exploitation of high capacity density battery has become the focus of research, and lithium metal has height
Theoretical specific capacity（3860mAh/g）, there is very big application potential in energy storage field, but the growth of Li dendrite, not only reduce
The performance of battery, and easily occur short circuit initiation potential safety hazard, these problems seriously hinder lithium anode secondary cell
Development and practical application.
Solve the above problems and relate generally to three aspects：Lithium metal, barrier film and electrolyte.It is concentrated mainly on the first two at present
Aspect, such as patent CN103384000A improve lithium secondary battery performance by designing a kind of method of 3D collector, pass through
Lithium metal is injected in a kind of skeleton with 3D structures electrode is made, this electrode will greatly reduce the local current of electrode
Density is so as to reach the effect of dendrite inhibition.But the method not only increase only the overall weight of battery, and preparation process is cumbersome,
It is unfavorable for commodity production.By contrast, it is a kind of simple and efficient way that corresponding nanometer additive is added into electrolyte.
The effect of current nanometer additive is mainly by participating in negative pole SEI formation so as to suppress lithium metal dendrite problems, and these are received
Rice additive generally fails gradually after circulation repeatedly, and the single nanometer additive of this kind of effect not can solve lithium gold
Belong to the dendrite problems of negative pole.Therefore, there is multiple inhibiting effect to receive lithium an- ode dendrite problems we have proposed a class
Rice fluoride is as the nonaqueous electrolytic solution of nanometer additive, and the system mechanism of action is many recasts using fluoride nano particles
The effect of the growth for the dendrite for suppressing lithium an- ode with reaching, current nanometer additive is solved to Li dendrite so that effective
The unconspicuous problem of inhibitory action.
In addition, having product to anode and barrier film respectively as the nonaqueous electrolytic solution of nanometer additive containing nano fluoride
Pole is acted on, so that battery has reached longer effect of more stable, safer, life-span.
The content of the invention
The purpose of the present invention is that have for above-mentioned deficiency of the prior art there is provided a kind of lithium an- ode dendrite problems
The compound of multiple inhibiting effect is used as nonaqueous electrolytic solution of nanometer additive and preparation method thereof and obtained lithium battery.
The purpose of the present invention is achieved through the following technical solutions：
A kind of electrolyte for suppressing Li dendrite, including lithium salts, nanometer additive, dispersant, organic solvent, the concentration of the lithium salts
For 0.5-10mol/L, the mass fraction of the dispersant is 0.01%-1%, and the mass fraction of the nanometer additive is 0.01%
~10%, wherein, the nanometer additive is LiF, CaF2、AlF3、NaF、MgF2、CsF2、KF、RbF、SrF2、PbF2、BeF2、
AgF、SnF2、BF3At least one of.
Above-mentioned fluoride nano particles are added in nonaqueous electrolytic solution, had to lithium an- ode, positive pole and barrier film respectively
Different facilitations, considers, and the nonaqueous electrolytic solution prepared using fluoride nano-particle as nanometer additive is made
Obtain battery and reach longer effect of more stable, safer, life-span.And the effect of the electrolyte of fluoride in the battery is
One continual and steady process, is contrasted with traditional film forming nanometer additive, and fluoride nano particles can reach in negative terminal surface
The effect of live fast filming, so as to effectively inhibit the growth of Li dendrite and the side reaction of positive electrode surface；Other fluoride
Nano-particle can be stabilized in the electrolytic solution, the appearance for the problems such as being failed in the absence of effect.
Wherein, the particle diameter of the nanometer additive is 5-20nm.Particle diameter is less than 5nm, and nanometer additive itself easily occurs
Reunite, film forming difficulty is high；Particle diameter is higher than 20nm, and the SEI film compactness of nanometer additive formation is poor.
Wherein, in addition to dispersant, the dispersant is CMC, PEG, neopelex, dodecyl sulphate
At least one of sodium, alkyl alcohol APEO, aliphatic amine polyoxyethylene ether.Dispersant can strengthen nanometer additive
Decentralization in organic solvent, improves the compactness of SEI films.
Preferably, the dispersant is CMC.
Wherein, the lithium salts is organic lithium salt and/or inorganic lithium salt.
Preferably, the inorganic lithium salt is LiPF6、LiClO4、LiBF4、LiBF3Cl、LiAsF6、LiNO3、LiI、LiCl、
At least one of LiBr；The organic lithium salt is LiCF3SO3、LiC4F9SO3、LiTFSI 、LiFSI 、LiFNFSI、LiIm
(BF3)、LiTADC、LiODFB、Li[(CF3)xBF4-x]、Li2B12F12 、Li2In DFB, LiMOB, LiTOP, LiFTOP at least
One kind, wherein x are natural number, 0≤x≤4.
Wherein, the organic solvent is lipid solvent, ether solvent, sulfone class solvent, sulfoxide type solvents, nitrile solvents, contained
At least one of phosphorus solvent.
Wherein, the lipid solvent is at least one of DMC, DEC, EC, PC, EMC, MPC, MiPC, GBL；The ether
Class solvent is at least one of THF, DOL, DME, DMM, TEGDME.
A kind of preparation method of electrolyte for suppressing Li dendrite as described above, comprises the following steps：（1）Lithium salts is dissolved in
In organic solvent, lithium salt solution is formed；（2）Other raw materials are added toward lithium salt solution, ultrasonic disperse 1-48 hours at 0-60 DEG C,
Obtain the electrolyte.
A kind of lithium battery for suppressing Li dendrite, including the electrolyte as described above for suppressing Li dendrite, in addition to positive plate,
Positive active material is coated with negative plate, barrier film, the positive plate, the positive active material aoxidizes for lithium transition-metal
At least one of thing, lithium transition-metal phosphoric acid thing, transition metal oxide, transient metal sulfide, conducting polymer.
It is further preferable that in order to suppress while Li dendrite, improving the high rate performance of lithium battery, the present invention also provides a kind of
The manufacturing process of high magnification positive plate, comprises the following steps：（1）The preparation of anode sizing agent：Toward 20-30 parts by weight N- methylpyrroles
Mixing is stirred after the adhesive of addition 3-5 parts by weight, the conductive agent of 1-2 parts by weight in alkanone, one-level slurry is obtained；It is past
Positive active material, 3-5 parts by weight conductive agent, the 2-5 weight of 100 parts by weight are added in 40-50 parts by weight 1-METHYLPYRROLIDONEs
Mixing is stirred after the Gemini surface active agent for measuring part, two grades of slurries are obtained；One-level slurry is added into two grades of slurries laggard
Row stirring mixing, obtains the anode sizing agent；（2）Film-making：Anode sizing agent and will be coated on positive plate, and dried, roller
Pressure, cutting.
The conductive agent of the application is 4-7 parts by weight, preferably 5.5 parts by weight.The effect of conductive agent is that providing electronics moves
Dynamic passage, the conductive agent of the application can obtain higher high rate performance and cycle performance in 5.5 parts by weight, and conductive agent is used
Amount is less than 4 parts by weight, and electron channel is few, is unfavorable for high current charge-discharge, the high rate performance of battery is not good, higher than 7 parts by weight, then
Easily occurring reunion causes crawling, and stability test is low and charge-discharge performance is not good, and electrode active material is relative
Reduction reduces battery capacity.
The application adhesive is 3-5 parts by weight, when adhesive is less than 3 parts by weight, although battery conductive better performances, still
The contact of positive active material and positive plate is poor, easily occurs the phenomenon that positive active material comes off, and stability is poor；Adhesive
During higher than 5 parts by weight, although the positive active material of the application, conductive agent is formed good three-dimensional conductive on positive plate
Network structure, but the insulating properties that adhesive has is so that the internal resistance increase of battery, electric conductivity declines.Preferably 4 parts by weight,
Electric conductivity and stability are preferable.
The application Gemini surface active agent is 2-5 parts by weight, when Gemini surface active agent is less than 2 parts by weight, does not have phase
It should act on, agglomeration easily occurs for anode sizing agent；During higher than 5 parts by weight, bubble is easily produced in whipping process, causes electricity
The easy entrained gas in pond and occur bulge phenomenon, and the consumption of Shuangzi activating agent is further improved, and castering action is simultaneously failed to understand
It is aobvious.
Wherein, the positive active material is LiNixCoyMnzO2, wherein 0.1≤x≤0.2,0.6≤y≤0.8,0.1≤
Z≤0.2, and x+y+z=1.The application Ni (NO3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2、LiOH·H2O is raw material,
New cobalt-nickel-manganese oxide compound is prepared using coprecipitation, with cost it is low, point position it is high, stability is strong the characteristics of, due to
Ni composition is less, it is not easy to which occurring analysis lithium phenomenon causes positive pole slurry pH value too high, thus hinder the stirring of anode sizing agent with
It is scattered, and in the presence of Fan Huadeli, the LiNi of the applicationxCoyMnzO2Easily with the Gemini surface active agent of the application
With reference to the stable anode sizing agent of formation.
Wherein, the preparation method of the conductive agent comprises the following steps：
A, every 1g CNT is added into volume ratio is 3：In 1 concentrated nitric acid and the lithium salt solution of the concentrated sulfuric acid, carry out at ultrasound
Manage 20-40min；
B and then progress reflow treatment 10-12h, reflux temperature is 80-90 DEG C；
C, standing, remove supernatant liquor, plus 1-METHYLPYRROLIDONE；
After D, repeat step C2-3 times, ultrasonic agitation is carried out, suction filtration is washed, dried, and grinding, the carbon after being surface-treated is received
Mitron；
E, the CNT after conducting polymer, the surface treatment is dissolved in DMF solvent, forms spinning solution, wherein, institute
Conducting polymer is stated at least one of polyacrylonitrile and polyacrylonitrile copolymer；
F, spinning solution is subjected to spinning, it is 20-25kV to control spinning voltage, and spinning temperature is 25-35 DEG C, obtains porous carbon and receives
Rice fiber；
G, the porous carbon nanofiber pre-oxidized into 2-3h at a temperature of 320-400 DEG C, the porous carbon after pre-oxidation is received
Rice fiber is placed in atmosphere of inert gases the carbonization that heats up, and carburizing temperature is 800-100 DEG C, and carbonization time is 1-2h, that is, obtains institute
The conductive agent stated.
The CNT of the application is after surface-active-treatment, and port is opened and forms the hydroxyl or carboxyl of activation,
The Fan Huade power improved with the application conducting polymer is acted on, and greatly reduces the sinking speed of CNT, and hinder it
Aggregation procedure, makes it be well dispersed in spinning process in porous carbon nanofiber.
Further, the step C is carried out under ultraviolet radiation environment, and the wavelength of the ultraviolet is 230-265nm.
Pass through further radiation treatment, it is possible to increase there is provided more active sites for the hydroxyl of CNT activation or the quantity of carboxyl
Point makes the porous carbon nanofiber of the application in combination, so as to improve the stability of positive pole slurries suspension system.
Further, the surface treated CNT is surface treated single-walled carbon nanotube.
Further, after the conducting polymer, the surface treatment CNT, the percent mass of DMF solvent
Respectively 5%-10%, 3%-7%, 83%-92%.
Further, the conducting polymer is by polyacrylonitrile, poly-（Acrylonitrile-pyrroles）, it is poly-（Acrylonitrile itaconic acid ammonium）
60-80 in molar ratio:10-20:10-20 ratio composition.It is poly-（Acrylonitrile-pyrroles）Cyclisation, oxygen occur in preoxidation process
The complex reaction such as change and dehydrogenation, molecular chain structure is changed, and is generated the conjugation polypyrrole of conductive energy, is enhanced and lead
The electric conductivity of electric polymer；But it is due to that preoxidation process is violent structure transformation period, easily produces defect, and follow-up
Charing can not correct pre-oxidation and stabilize the defect brought, and can step by step amplify on the contrary, cause conducting polymer to be formed
Even conductive network, easily occurs partial short-circuit and increases the loss and heating of lithium battery, and gathers（Acrylonitrile itaconic acid ammonium）In
Comonomer itaconic acid ammonium significantly reduce exothermic peak initial temperature and thermal discharge of the polyacrylonitrile in preoxidation process, make
Exothermic peak is widened, and is helped to control preoxidation process, is reduced the formation of defect, so as to form stable lead with positive active material
Electric network.It is further preferable that the conducting polymer is by polyacrylonitrile, poly-（Acrylonitrile-pyrroles）, it is poly-（Acrylonitrile itaconic acid
Ammonium）In molar ratio 66:16:18 ratio composition.
Wherein, the Gemini surface active agent is by with structural formula（Ⅰ）Alkylbenzenesulfonate Gemini surface active agent and tool
There is structural formula（Ⅱ）Quaternary ammonium type Gemini surface active agent composition：
Structural formula（Ⅰ）
Structural formula（Ⅱ）
The Gemini surface active agent of the application is respectively containing single phenyl ring and double benzene ring structures, and benzene ring structure contributes to the application conductive
Agent is scattered in water, that is to say that two kinds of Gemini surface active agents can individual play the effect of conductive agent, but both are multiple
That matches somebody with somebody is better.
It is further preferred that the Gemini surface active agent is by with structural formula（Ⅰ）Live on alkylbenzenesulfonate Shuangzi surface
Property agent and with structural formula（Ⅱ）Quaternary ammonium type Gemini surface active agent by weight 2-3:4-6 ratio composition.
It is further preferred that the Gemini surface active agent is by with structural formula（Ⅰ）Alkylbenzenesulfonate Shuangzi surface
Activating agent and with structural formula（Ⅱ）Quaternary ammonium type Gemini surface active agent by weight 1:2 ratio composition.
Described adhesive is polytetrafluoroethylene (PTFE) and butadiene-styrene rubber by weight 3:The mixture of 1 composition.Polytetrafluoroethylene (PTFE) and
Butadiene-styrene rubber is respectively provided with cohesive, and exclusive use can play adhesive effect, but be due to that polytetrafluoroethylene (PTFE) and butadiene-styrene rubber are equal
Without electric conductivity, ratio and consumption are to cause the change of the performances such as lithium battery irreversible capacity, and the application is directed to
LiNixCoyMnzO2The restructuring experiment of adhesive is carried out, is finally given with polytetrafluoroethylene (PTFE) and butadiene-styrene rubber by weight 3:1 group
Into adhesive component, the adhesive can be such that the positive active material of the application is bonded with positive plate, have substantially no effect on simultaneously
The electric conductivity of the application lithium battery.
Wherein, the positive plate is aluminium foil, and the coating thickness of anode sizing agent is 10-25 μm, and coated face density is 23-
26mg/cm2。
Beneficial effects of the present invention：The present invention is preferential in lithium an- ode table by using sl. sol. fluoride nano particles
Face deposits to form one layer of passivating film to negative pole formation protective effect and use the cation of slightly soluble fluoride due to electrostatic screen
Effect promotes lithium ion in negative pole uniform deposition, the SEI film even compacts of formation, so as to inhibit dendrite problems.Furthermore, its is attached
And the security that a kind of similar " ceramic diaphragm " adds battery is formed in barrier film both sides, and, fluorine similar with lithium an- ode
The addition of compound is same positive pole is formed stable passivating film play the role of it is positive, so as to inhibit the side reaction of positive electrode surface.
The effect of the electrolyte of fluoride in the battery is a continual and steady process, is contrasted with traditional film forming nanometer additive,
Fluoride nano particles can reach the effect of live fast filming in negative terminal surface, so as to effectively inhibit the growth of Li dendrite
And the side reaction of positive electrode surface；Other fluoride nano particles can be stabilized in the electrolytic solution, be failed in the absence of effect
The problems such as appearance.
Brief description of the drawings
Fig. 1 is that the present invention carries out testing obtained when m- voltage pattern to Li Shu Li Symmetrical cells made from embodiment 1；
Fig. 2 is that the present invention carries out testing obtained when m- voltage pattern to Li Shu Li Symmetrical cells made from comparative example 1；
Fig. 3 is that the present invention carries out testing obtained when m- voltage pattern to Li Shu Li Symmetrical cells made from embodiment 2；
Fig. 4 is that the present invention carries out testing obtained when m- voltage pattern to Li Shu Li Symmetrical cells made from comparative example 2；
Fig. 5 is the pattern of Li Shu Cu battery copper foil depositions 1h made from embodiment 1；
Fig. 6 is the pattern of Li Shu Cu battery copper foil depositions 1h made from comparative example 1；
Fig. 7 is the pattern of Li Shu Cu battery copper foil depositions 1h made from embodiment 2；
Fig. 8 is the pattern of Li Shu Cu battery copper foil depositions 1h made from comparative example 2；
Fig. 9 is specific capacity-circulation figure for embodiment 5 and comparative example 3.
Embodiment
The invention will be further described with the following Examples.
Embodiment 1
A kind of electrolyte for suppressing Li dendrite, including lithium salts, nanometer additive, organic solvent, the concentration of the lithium salts is 1mol/
L, the mass fraction of the nanometer additive is 0.1%, and the mass fraction of the dispersant is 0.1%.
Wherein, the nanometer additive is LiF；The dispersant is CMC；The organic solvent is by 1,3- dioxolanes
（DOL）And glycol dimethyl ether（DME）By volume 1:1 ratio composition；The lithium salts is double（Fluoro sulphonyl）Imine lithium
（LiFSI）.
Its preparation method comprises the following steps：（1）Lithium salts is dissolved in organic solvent, lithium salt solution is formed；（2）Toward lithium
Salting liquid adds other raw materials, and ultrasonic disperse 2 hours at 25 DEG C obtain the electrolyte.
（2）The installation of Li Shu Li Symmetrical cells：Battery hull specification used is 2032.According to positive electrode shell-lithium metal piece
（φ=16mm）- electrolyte-barrier film-electrolyte-lithium metal piece（φ=16mm）- pad（2）- shell fragment（1）- negative electrode shell
Order is installed.Wherein, the volume of electrolyte used is 80 μ L, each 40 μ L in barrier film both sides.By mounted battery at normal temperatures
Stand 12 hours.
（3）The installation of Li Shu Cu batteries：Clean copper foil is cut into a diameter of 12mm copper sheet with sanction pole piece machine, put
Soak 10 minutes, then cleaned 4 times with deionized water in 1.0mol/L hydrochloric acid, finally copper sheet is placed in absolute ethyl alcohol and soaked
It is 5 minutes, rapid to dry, it is immediately transferred in the glove box full of argon gas.Lithium piece is washed into a diameter of 12mm's in glove box
Pole piece.According to positive electrode shell-copper sheet（φ=12mm）- electrolyte-barrier film-electrolyte-lithium metal piece（φ=12mm）- pad（2
It is individual）- shell fragment（1）- negative electrode shell.The amount of same electrolyte used is 80 μ L, each 40 μ L in barrier film both sides.By mounted battery
Stand 12 hours at normal temperatures.
（4）Li Shu Li Symmetrical cells are tested：The environment of test is the rich battery test system of Wuhan indigo plant.Constant current discharge charge in test
The current density I of electricity is 2.0mA.cm-2, and charge density Q is 1.0mAh.cm-2.
（5）Li Shu Cu battery efficiencies are tested：First low current activation, the current density of activation is 0.05mA.cm-2, voltage range
For 0.010-1.000V, activate 5 times.Then charge-discharge test is carried out, constant current charge/discharge current density is 1.0mA.cm-2, voltage
For 1.000V.
（6）SEM is tested：The Li Shu Cu batteries for depositing 1.0h are taken apart in glove box, takes out the copper foil in battery, is placed on
Clean up, dried under vacuum in DME, the last quick copper foil of wash clean is taken away carries out SEM observations.
Embodiment 2
A kind of electrolyte for suppressing Li dendrite, including lithium salts, nanometer additive, organic solvent, the concentration of the lithium salts is 1mol/
L, the mass fraction of the nanometer additive is 1%, and the mass fraction of the dispersant is 0.1%.
Wherein, the nanometer additive is CsF；The dispersant is CMC；The organic solvent is by 1,3- dioxolanes
（DOL）And glycol dimethyl ether（DME）By volume 1:1 ratio composition；The lithium salts is lithium hexafluoro phosphate (LiPF6)。
Its preparation method comprises the following steps：（1）Lithium salts is dissolved in organic solvent, lithium salt solution is formed；（2）Toward lithium
Salting liquid adds other raw materials, and ultrasonic disperse 2 hours at 25 DEG C obtain the electrolyte.
Comparative example 1
The difference of this comparative example and embodiment 1 is：The electrolyte of this comparative example 1 is free of nanometer additive and dispersant.
Comparative example 2
The difference of this comparative example and embodiment 2 is：The electrolyte of this comparative example 2 is free of nanometer additive and dispersant.
Embodiment 1-2 and comparative example 1-2 are assembled into the installation of Li Shu Li Symmetrical cells and Li Shu Cu batteries by the present invention, enter
And carry out performance test.
The installation method of Li Shu Li Symmetrical cells：Battery hull specification used is 2032.According to positive electrode shell-lithium metal piece
（φ=16mm）- electrolyte-barrier film-electrolyte-lithium metal piece（φ=16mm）- pad（2）- shell fragment（1）- negative electrode shell
Order is installed.Wherein, the volume of electrolyte used is 80 μ L, each 40 μ L in barrier film both sides.By mounted battery at normal temperatures
Stand 12 hours.
The installation method of Li Shu Cu batteries：Clean copper foil is cut into a diameter of 12mm copper sheet with sanction pole piece machine, put
Soak 10 minutes, then cleaned 4 times with deionized water in 1.0mol/L hydrochloric acid, finally copper sheet is placed in absolute ethyl alcohol and soaked
It is 5 minutes, rapid to dry, it is immediately transferred in the glove box full of argon gas.Lithium piece is washed into a diameter of 12mm's in glove box
Pole piece.According to positive electrode shell-copper sheet（φ=12mm）- electrolyte-barrier film-electrolyte-lithium metal piece（φ=12mm）- pad（2
It is individual）- shell fragment（1）- negative electrode shell.The amount of same electrolyte used is 80 μ L, each 40 μ L in barrier film both sides.By mounted battery
Stand 12 hours at normal temperatures.
Li Shu Li Symmetrical cells method of testings：The environment of test is the rich battery test system of Wuhan indigo plant.In test constant current fill/
The current density I of electric discharge is 2.0mA.cm-2, and charge density Q is 1.0mAh.cm-2.
Li Shu Cu battery efficiency method of testings：First low current activation, the current density of activation is 0.05mA.cm-2, voltage model
Enclose for 0.010-1.000V, activation 5 times.Then charge-discharge test is carried out, constant current charge/discharge current density is 1.0mA.cm-2, electricity
Press as 1.000V.Then the Li Shu Cu batteries for depositing 1.0h are taken apart in glove box, takes out the copper foil in battery, be placed in DME
Clean up, dried under vacuum, the last quick copper foil of wash clean is taken away carries out SEM observations.
Such as Fig. 1-4, respectively embodiment 1, comparative example 1, embodiment 2, Li Shu Li Symmetrical cells made from comparative example 2 are measured
When m- voltage pattern.Comparison diagram 1 and Fig. 2 can be seen that under the conditions of same test, add the electrolyte of LiF nano-particles,
The polarizing voltage very little of Symmetrical cells and very stable, illustrates that the electrolyte containing fluoride nano particles forms even compact
SEI films, have critically important inhibitory action to the formation of Li dendrite.Fig. 3 and Fig. 4 further illustrate this conclusion.
Such as Fig. 5-8, respectively embodiment 1, comparative example 1, embodiment 2, Li Shu Cu battery copper foil depositions made from comparative example 2
1h pattern.Comparison diagram 5 and Fig. 6, it can be seen that added the electrolyte of fluoride to inhibit lithium well in lithium deposition process
The dendrite problems of metal, are not added with the dendrite of the electrolyte formation needle-like of LiF nano-particles, and have added the electrolyte of fluoride not have
There is needle-like pattern.Fig. 7 and Fig. 8 contrasts further illustrate this conclusion.
Embodiment 3
A kind of electrolyte for suppressing Li dendrite, including lithium salts, nanometer additive, organic solvent, the concentration of the lithium salts is
10mol/L, the mass fraction of the nanometer additive is 0.01%, and the mass fraction of the dispersant is 0.01%.
Wherein, the nanometer additive is by AlF3、NaF、MgF2By weight 1：1：1 ratio composition；The dispersant is
PEG；The organic solvent is by DMC, DEC, EC by volume 1：1：1 ratio composition；The lithium salts is LiPF6、LiClO4、
LiBF4、LiBF3Cl is by weight 1：1：1：1 ratio composition.
Its preparation method comprises the following steps：（1）Lithium salts is dissolved in organic solvent, lithium salt solution is formed；（2）Toward lithium
Salting liquid adds other raw materials, and ultrasonic disperse 48 hours at 0 DEG C obtain the electrolyte.
Embodiment 4
A kind of electrolyte for suppressing Li dendrite, including lithium salts, nanometer additive, organic solvent, the concentration of the lithium salts is 2mol/
L, the mass fraction of the nanometer additive is 0.01%, and the mass fraction of the dispersant is 0.01%.
Wherein, the nanometer additive is by KF, RbF, SrF2、PbF2、BeF2, AgF is by weight 1：1：1：1:1:1 ratio
Example composition；The dispersant is neopelex, lauryl sodium sulfate, alkyl alcohol APEO, fat
Amine APEO is by weight 1:1:1:1 ratio composition；The organic solvent is by THF, DOL, DME, DMM by volume 1：
1：1：1 ratio composition；The lithium salts is by LiCF3SO3、LiC4F9SO3, LiTFSI, LiFSI, LiFNFSI be by weight 1：1：
1：1：1 ratio composition.
Its preparation method comprises the following steps：（1）Lithium salts is dissolved in organic solvent, lithium salt solution is formed；（2）Toward lithium
Salting liquid adds other raw materials, and ultrasonic disperse 1 hour at 60 DEG C obtains the electrolyte.
Embodiment 5
A kind of lithium battery for suppressing Li dendrite, includes electrolyte, positive plate, negative plate, the barrier film of embodiment 1, the positive plate
Preparation method be：30mg adhesive PVDFs addition 0.5ml 1-METHYLPYRROLIDONEs NMP is weighed to stir under magnetic stirring apparatus
Half an hour.Positive active material is weighed again, and the positive active material is by 30mg activated carbon and 240mg LiFePO4 groups
Into being mixed to be placed in mortar and grind uniform, pour into afterwards scattered containing 30mg adhesive PVDFs with 0.5ml
In the reaction bulb of 1-METHYLPYRROLIDONE, 24h is stirred at 25 DEG C.After slurry agitation is uniform, from specification scraping for 150mm
Knife is coated on aluminium foil, is placed on 110 DEG C of baking 12h of vacuum drying oven.
The preparation method of lithium battery is：Electricity is filled in water content and the equal ＜ 0.1ppm of the oxygen content glove box full of argon gas
Pond, according to anode cover-positive plate (φ=12mm)-electrolyte-barrier film-electrolyte-lithium piece (φ=16mm)-pad-negative electrode casing
Order installs battery, is encapsulated with tablet press machine.Static 12 hours at room temperature.The amount of the electrolyte of embodiment 1 used is 80 μ
L, each 40 μ L in barrier film both sides.Mounted battery is stood 12 hours using its cyclical stability of blue electrical measurement, permanent electricity at normal temperatures
Flow discharge and recharge, 0.5C（1C=170mA/g）, potential window is 2.5~4.2.
Comparative example 3
The difference of this comparative example and embodiment 5 is：The electrolyte used for comparative example 1 electrolyte.
It is respectively the specific capacity-circulation figure, Fig. 9 of embodiment 5 and comparative example 3 in upper curve and the curve under such as Fig. 9
Comparative illustration, adds LiF and the performance of positive pole is greatly improved, and illustrates to add fluoride nano particles to suppressing positive electrode
Dissolving be very helpful.
Embodiment 6
The present embodiment and the difference of embodiment 5 are：
The preparation method of the positive plate comprises the following steps：（1）4 parts by weight are added into 25 parts by weight 1-METHYLPYRROLIDONEs
Adhesive, be stirred mixing after the conductive agent of 1.5 parts by weight, obtain one-level slurry；Toward 45 parts by weight N- crassitudes
The Gemini surface active agent that the positive active material, the conductive agent of 4 parts by weight, 3.5 parts by weight of 50 parts by weight are added in ketone is laggard
Row stirring mixing, obtains two grades of slurries；Mixing is stirred after adding one-level slurry into two grades of slurries, the positive pole slurry is obtained
Material；（2）Anode sizing agent and will be coated on positive plate, and dried, roll-in, cutting.
Wherein, the positive active material is LiNixCoyMnzO2, wherein x=0.15, y=0.7, z=0.15.
Wherein, described adhesive is polytetrafluoroethylene (PTFE) and butadiene-styrene rubber by weight 3:The mixture of 1 composition.
Wherein, the preparation method of the conductive agent comprises the following steps：
A, every 1g CNT is added into volume ratio is 3：In 1 concentrated nitric acid and the lithium salt solution of the concentrated sulfuric acid, carry out at ultrasound
Manage 20-40min；
B and then progress reflow treatment 11h, reflux temperature is 85 DEG C；
C, standing, remove supernatant liquor, plus 1-METHYLPYRROLIDONE；
After D, repeat step C3 times, ultrasonic agitation is carried out, suction filtration is washed, dried, grinding, the carbon nanometer after be surface-treated
Pipe.
E, the CNT after conducting polymer, the surface treatment is dissolved in DMF solvent, forms spinning solution；
F, spinning solution is subjected to spinning, it is 22.5kV to control spinning voltage, and spinning temperature is 30 DEG C, obtains porous carbon Nanowire
Dimension；
G, the porous carbon nanofiber pre-oxidized into 2.5h at a temperature of 360 DEG C, by the porous carbon Nanowire after pre-oxidation
Dimension is placed in atmosphere of inert gases the carbonization that heats up, and carburizing temperature is 900 DEG C, and carbonization time is 1.5h, that is, obtains described conduction
Agent.
Wherein, the step C is carried out under ultraviolet radiation environment, and the wavelength of the ultraviolet is 245nm.
Wherein, after the conducting polymer, the surface treatment CNT, the percent mass difference of DMF solvent
For 7.5%, 5%, 87.5%.
Wherein, the conducting polymer is by polyacrylonitrile, poly-（Acrylonitrile-pyrroles）, it is poly-（Acrylonitrile itaconic acid ammonium）Massage
You compare 66:16:18 ratio composition.
Wherein, the Gemini surface active agent is by with structural formula（Ⅰ）Alkylbenzenesulfonate Gemini surface active agent and tool
There is structural formula（Ⅱ）Quaternary ammonium type Gemini surface active agent by weight 1:2 ratio composition.
Wherein, the positive plate is aluminium foil, and the coating thickness of anode sizing agent is 17.5 μm, and coated face density is 24.5mg/
cm2.Embodiment 7
The present embodiment and the difference of embodiment 6 are：
The preparation method of the positive plate comprises the following steps：（1）3 parts by weight are added into 20 parts by weight 1-METHYLPYRROLIDONEs
Adhesive, be stirred mixing after the conductive agent of 1 parts by weight, obtain one-level slurry；Toward 40 parts by weight 1-METHYLPYRROLIDONEs
Stirred after the middle positive active material, the conductive agent of 3 parts by weight, the Gemini surface active agent of 2 parts by weight for adding 100 parts by weight
Mixing is mixed, two grades of slurries are obtained；Mixing is stirred after adding one-level slurry into two grades of slurries, the anode sizing agent is obtained；
（2）Anode sizing agent and will be coated on positive plate, and dried, roll-in, cutting.
Wherein, the positive active material is LiNixCoyMnzO2, wherein x=0.1, y=0.8, z=0.1.
Wherein, described adhesive is polytetrafluoroethylene (PTFE) and butadiene-styrene rubber by weight 2:The mixture of 1 composition.
Wherein, the preparation method of the conductive agent comprises the following steps：
A, every 1g CNT is added into volume ratio is 3：In 1 concentrated nitric acid and the lithium salt solution of the concentrated sulfuric acid, carry out at ultrasound
Manage 20-40min；
B and then progress reflow treatment 10h, reflux temperature is 80 DEG C；
C, standing, remove supernatant liquor, plus 1-METHYLPYRROLIDONE；
After D, repeat step C2 times, ultrasonic agitation is carried out, suction filtration is washed, dried, grinding, the carbon nanometer after be surface-treated
Pipe.
E, the CNT after conducting polymer, the surface treatment is dissolved in DMF solvent, forms spinning solution；
F, spinning solution is subjected to spinning, it is 20kV to control spinning voltage, and spinning temperature is 25 DEG C, obtains porous carbon Nanowire
Dimension；
G, the porous carbon nanofiber pre-oxidized into 2h at a temperature of 320 DEG C, by the porous carbon nanofiber after pre-oxidation
The carbonization that heats up is placed in atmosphere of inert gases, and carburizing temperature is 800 DEG C, and carbonization time is 1h, that is, obtains described conductive agent.
Wherein, the step C is carried out under ultraviolet radiation environment, and the wavelength of the ultraviolet is 230nm.
Wherein, after the conducting polymer, the surface treatment CNT, the percent mass difference of DMF solvent
For 5%%, 3%%, 92%.
Wherein, the conducting polymer is by polyacrylonitrile, poly-（Acrylonitrile-pyrroles）, it is poly-（Acrylonitrile itaconic acid ammonium）Massage
You compare 60: 20:20 ratio composition.
Wherein, the Gemini surface active agent is by with structural formula（Ⅰ）Alkylbenzenesulfonate Gemini surface active agent and tool
There is structural formula（Ⅱ）Quaternary ammonium type Gemini surface active agent by weight 1:3 ratio composition.
Wherein, the positive plate is aluminium foil, and the coating thickness of anode sizing agent is 10 μm, and coated face density is 23mg/cm2。
Embodiment 8
The present embodiment and the difference of embodiment 6 are：
The preparation method of the positive plate comprises the following steps：（1）5 parts by weight are added into 30 parts by weight 1-METHYLPYRROLIDONEs
Adhesive, be stirred mixing after the conductive agent of 2 parts by weight, obtain one-level slurry；Toward 50 parts by weight 1-METHYLPYRROLIDONEs
Stirred after the middle positive active material, the conductive agent of 5 parts by weight, the Gemini surface active agent of 5 parts by weight for adding 100 parts by weight
Mixing is mixed, two grades of slurries are obtained；Mixing is stirred after adding one-level slurry into two grades of slurries, the anode sizing agent is obtained；
（2）Anode sizing agent and will be coated on positive plate, and dried, roll-in, cutting.
Wherein, the positive active material is LiNixCoyMnzO2, wherein x=0.2, y=0.6, z=0.2.
Wherein, described adhesive is polytetrafluoroethylene (PTFE) and butadiene-styrene rubber by weight 1:The mixture of 1 composition.
Wherein, the preparation method of the conductive agent comprises the following steps：
A, every 1g CNT is added into volume ratio is 3：In 1 concentrated nitric acid and the lithium salt solution of the concentrated sulfuric acid, carry out at ultrasound
Manage 40min；
B and then progress reflow treatment 12h, reflux temperature is 90 DEG C；
C, standing, remove supernatant liquor, plus 1-METHYLPYRROLIDONE；
After D, repeat step C3 times, ultrasonic agitation is carried out, suction filtration is washed, dried, grinding, the carbon nanometer after be surface-treated
Pipe.
E, the CNT after conducting polymer, the surface treatment is dissolved in DMF solvent, forms spinning solution, its
Described in conducting polymer be at least one of polyacrylonitrile and polyacrylonitrile copolymer；
F, spinning solution is subjected to spinning, it is 25kV to control spinning voltage, and spinning temperature is 35 DEG C, obtains porous carbon Nanowire
Dimension；
G, the porous carbon nanofiber pre-oxidized into 3h at a temperature of 400 DEG C, by the porous carbon nanofiber after pre-oxidation
The carbonization that heats up is placed in atmosphere of inert gases, and carburizing temperature is 100 DEG C, and carbonization time is 2h, that is, obtains described conductive agent.
Wherein, the step C is carried out under ultraviolet radiation environment, and the wavelength of the ultraviolet is 265nm.
Wherein, after the conducting polymer, the surface treatment CNT, the percent mass difference of DMF solvent
For 10%, 7%, 83%.
Wherein, the conducting polymer is by polyacrylonitrile, poly-（Acrylonitrile-pyrroles）, it is poly-（Acrylonitrile itaconic acid ammonium）Massage
You compare 80:10:10 ratio composition.
Wherein, the Gemini surface active agent is by with structural formula（Ⅰ）Alkylbenzenesulfonate Gemini surface active agent and tool
There is structural formula（Ⅱ）Quaternary ammonium type Gemini surface active agent by weight 3:4 ratio composition.
Wherein, the positive plate is aluminium foil, and the coating thickness of anode sizing agent is 25 μm, and coated face density is 26mg/cm2。
Embodiment 9
The present embodiment and the difference of embodiment 6 are：
The preparation method of the positive plate comprises the following steps：（1）4 weights are added into 20-30 parts by weight 1-METHYLPYRROLIDONEs
Mixing is stirred after measuring the adhesive of part, the conductive agent of 1.8 parts by weight, one-level slurry is obtained；Toward 44 parts by weight N- methyl pyrroles
The positive active material, the conductive agent of 3.5 parts by weight, the Gemini surface active of 4.5 parts by weight of 100 parts by weight are added in pyrrolidone
Mixing is stirred after agent, two grades of slurries are obtained；Mixing is stirred after adding one-level slurry into two grades of slurries, obtains described
Anode sizing agent；（2）Anode sizing agent and will be coated on positive plate, and dried, roll-in, cutting.
Wherein, the positive active material is LiNixCoyMnzO2, wherein x=0.2, y=0.7, z=0.1.
Wherein, described adhesive is polytetrafluoroethylene (PTFE).
Wherein, the preparation method of the conductive agent comprises the following steps：
A, every 1g CNT is added into volume ratio is 3：In 1 concentrated nitric acid and the lithium salt solution of the concentrated sulfuric acid, carry out at ultrasound
Manage 20-40min；
B and then progress reflow treatment 12h, reflux temperature is 90 DEG C；
C, standing, remove supernatant liquor, plus 1-METHYLPYRROLIDONE；
After D, repeat step C3 times, ultrasonic agitation is carried out, suction filtration is washed, dried, grinding, the carbon nanometer after be surface-treated
Pipe.
E, the CNT after conducting polymer, the surface treatment is dissolved in DMF solvent, forms spinning solution；
F, spinning solution is subjected to spinning, it is 24kV to control spinning voltage, and spinning temperature is 32 DEG C, obtains porous carbon Nanowire
Dimension；
G, the porous carbon nanofiber pre-oxidized into 2.2h at a temperature of 370 DEG C, by the porous carbon Nanowire after pre-oxidation
Dimension is placed in atmosphere of inert gases the carbonization that heats up, and carburizing temperature is 850 DEG C, and carbonization time is 1.2h, that is, obtains described conduction
Agent.
Wherein, the step C is carried out under ultraviolet radiation environment, and the wavelength of the ultraviolet is 240nm.
Wherein, after the conducting polymer, the surface treatment CNT, the percent mass difference of DMF solvent
For 7%, 4%, 89%.
Wherein, the conducting polymer is by polyacrylonitrile, poly-（Acrylonitrile-pyrroles）, it is poly-（Acrylonitrile itaconic acid ammonium）Massage
You compare 74:11:15 ratio composition.
Wherein, the Gemini surface active agent is with structural formula（Ⅰ）Alkylbenzenesulfonate Gemini surface active agent.
Wherein, the positive plate is aluminium foil, and the coating thickness of anode sizing agent is 14 μm, and coated face density is 25mg/cm2。
Embodiment 10
The present embodiment and the difference of embodiment 6 are：
The preparation method of the positive plate comprises the following steps：（1）3.5 weight are added into 23 parts by weight 1-METHYLPYRROLIDONEs
Part adhesive, be stirred mixing after the conductive agent of 1.2 parts by weight, obtain one-level slurry；Toward 43 parts by weight N- methylpyrroles
After positive active material, the conductive agent of 4.2 parts by weight, the Gemini surface active agent of 4 parts by weight that 100 parts by weight are added in alkanone
Mixing is stirred, two grades of slurries are obtained；Mixing is stirred after adding one-level slurry into two grades of slurries, the positive pole is obtained
Slurry；（2）Anode sizing agent and will be coated on positive plate, and dried, roll-in, cutting.
Wherein, the positive active material is LiNixCoyMnzO2, wherein x=1/3, y=1/3, z=1/3.
Wherein, described adhesive is polytetrafluoroethylene (PTFE) and butadiene-styrene rubber by weight 3:The mixture of 1 composition.
Wherein, the preparation method of the conductive agent comprises the following steps：
A, every 1g CNT is added into volume ratio is 3：In 1 concentrated nitric acid and the lithium salt solution of the concentrated sulfuric acid, carry out at ultrasound
Manage 20-40min；
B and then progress reflow treatment 11.5h, reflux temperature is 78 DEG C；
C, standing, remove supernatant liquor, plus 1-METHYLPYRROLIDONE；
After D, repeat step C3 times, ultrasonic agitation is carried out, suction filtration is washed, dried, grinding, the carbon nanometer after be surface-treated
Pipe.
E, the CNT after conducting polymer, the surface treatment is dissolved in DMF solvent, forms spinning solution, its
Described in conducting polymer be polyacrylonitrile；
F, spinning solution is subjected to spinning, it is 21kV to control spinning voltage, and spinning temperature is 31 DEG C, obtains porous carbon Nanowire
Dimension；
G, the porous carbon nanofiber pre-oxidized into 2.7h at a temperature of 320-400 DEG C, the porous carbon after pre-oxidation is received
Rice fiber is placed in atmosphere of inert gases the carbonization that heats up, and carburizing temperature is 930 DEG C, and carbonization time is 1.7h, that is, obtains described
Conductive agent.
Wherein, the step C is carried out under ultraviolet radiation environment, and the wavelength of the ultraviolet is 260nm.
Wherein, after the conducting polymer, the surface treatment CNT, the percent mass difference of DMF solvent
For 8%, 4%, 88%.
Wherein, the Gemini surface active agent is with structural formula（Ⅱ）Quaternary ammonium type Gemini surface active agent.
Wherein, the positive plate is aluminium foil, and the coating thickness of anode sizing agent is 22 μm, and coated face density is 24mg/cm2。
Embodiment 11
The present embodiment and the difference of embodiment 6 are：
The preparation method of the positive plate comprises the following steps：（1）3 parts by weight are added into 27 parts by weight 1-METHYLPYRROLIDONEs
Adhesive, be stirred mixing after the conductive agent of 2 parts by weight, obtain one-level slurry；Toward 43 parts by weight 1-METHYLPYRROLIDONEs
Carried out after the middle positive active material, the conductive agent of 4.5 parts by weight, the Gemini surface active agent of 3 parts by weight for adding 100 parts by weight
Stirring mixing, obtains two grades of slurries；Mixing is stirred after adding one-level slurry into two grades of slurries, the positive pole slurry is obtained
Material；（2）Anode sizing agent and will be coated on positive plate, and dried, roll-in, cutting.
Wherein, the positive active material is LiNixCoyMnzO2, wherein x=0.2, y=0.65, z=0.15.
Wherein, described adhesive is polytetrafluoroethylene (PTFE) and butadiene-styrene rubber by weight 4:The mixture of 1 composition.
Wherein, the conductive agent passes through ultrasonic dispersion and solvent deposition legal system by porous carbon nanofiber and CNT
.
Wherein, the Gemini surface active agent is by with structural formula（Ⅰ）Alkylbenzenesulfonate Gemini surface active agent and tool
There is structural formula（Ⅱ）Quaternary ammonium type Gemini surface active agent by weight 2.5:6 ratio composition.
Wherein, the positive plate is aluminium foil, and the coating thickness of anode sizing agent is 12 μm, and coated face density is 23.5mg/
cm2。
By the way that the electrolyte of embodiment 6-11 positive plate and graphite negative electrode, embodiment 1 constituted into lithium battery, and by lithium
After battery is charged, 3.0V is discharged to 3C, 2C, 1C, 0.1C continuous discharge respectively, the discharge capacity of different electric currents is recorded,
And then calculate 3C（3C capacity/0.3C capacity）、2C（2C capacity/0.2C capacity）、1C（1C capacity/0.1C capacity）Electric discharge times
Rate, obtains following performance test table：
The anode sizing agent obtained by the application method is uniform and stable without particle bubble-free, as seen from the above table, embodiment 6-11's
Anode sizing agent obtains fully dispersed and forms good conductive network structure, the capacitance and discharge-rate of obtained lithium battery
Certain raising is obtained, and passes through multiple discharge cycle test, after the embodiment of the present application 1-6 1C/1C is circulated 500 times
Capacity reach more than 97%.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than to present invention guarantor
The limitation of scope is protected, although being explained with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Work as understanding, technical scheme can be modified or equivalent substitution, without departing from the reality of technical solution of the present invention
Matter and scope.
Claims (10)
1. a kind of electrolyte for suppressing Li dendrite, it is characterised in that：Including lithium salts, nanometer additive, dispersant and organic solvent,
The concentration of the lithium salts is 0.5-10mol/L, and the mass fraction of the nanometer additive is 0.01%~10%, the dispersant
Mass fraction be 0.01%-1%, wherein, the nanometer additive be LiF, CaF2、AlF3、NaF、MgF2、CsF2、KF、RbF、
SrF2、PbF2、BeF2、AgF、SnF2And BF3At least one of.
2. a kind of electrolyte for suppressing Li dendrite according to claim 1, it is characterised in that：The grain of the nanometer additive
Footpath is 5-20nm.
3. a kind of electrolyte for suppressing Li dendrite according to claim 1, it is characterised in that：The dispersant be CMC,
In PEG, neopelex, lauryl sodium sulfate, alkyl alcohol APEO and aliphatic amine polyoxyethylene ether
At least one.
4. a kind of electrolyte for suppressing Li dendrite according to claim 3, it is characterised in that：The dispersant is CMC.
5. a kind of electrolyte for suppressing Li dendrite according to claim 1, it is characterised in that：The lithium salts is organic lithium salt
And/or inorganic lithium salt.
6. a kind of electrolyte for suppressing Li dendrite according to claim 5, it is characterised in that：The inorganic lithium salt is
LiPF6、LiClO4、LiBF4、LiBF3Cl、LiAsF6、LiNO3, at least one of LiI, LiCl and LiBr；The organic lithium salt
For LiCF3SO3、LiC4F9SO3、LiTFSI 、LiFSI 、LiFNFSI、LiIm(BF3)、LiTADC、LiODFB、Li[(CF3)xBF4-x]、Li2B12F12 、Li2At least one of DFB, LiMOB, LiTOP and LiFTOP, wherein x are natural number, 0≤x≤4.
7. a kind of electrolyte for suppressing Li dendrite according to claim 1, it is characterised in that：The organic solvent is lipid
At least one of solvent, ether solvent, sulfone class solvent, sulfoxide type solvents, nitrile solvents and phosphorous solvent.
8. a kind of electrolyte for suppressing Li dendrite according to claim 1, it is characterised in that：The lipid solvent be DMC,
At least one of DEC, EC, PC, EMC, MPC, MiPC and GBL；The ether solvent is THF, DOL, DME, DMM and TEGDME
At least one of.
9. a kind of preparation method of the electrolyte of suppression Li dendrite as described in claim 1-8 any one, it is characterised in that：
Comprise the following steps：（1）Lithium salts is dissolved in organic solvent, lithium salt solution is formed；（2）Other raw materials are added toward lithium salt solution,
The ultrasonic disperse 1-48h at a temperature of 0-60 DEG C, that is, obtain the electrolyte.
10. a kind of lithium battery for suppressing Li dendrite, it is characterised in that：Including the suppression as described in claim 1-8 any one
Be coated with positive active material on the electrolyte of Li dendrite, in addition to positive plate, negative plate, barrier film, the positive plate, it is described just
Pole active material be lithium transition-metal oxide, lithium transition-metal phosphoric acid thing, transition metal oxide, transient metal sulfide and
At least one of conducting polymer.
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