CN109449486A - A kind of application of electrolysis additive - Google Patents
A kind of application of electrolysis additive Download PDFInfo
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- CN109449486A CN109449486A CN201811194944.1A CN201811194944A CN109449486A CN 109449486 A CN109449486 A CN 109449486A CN 201811194944 A CN201811194944 A CN 201811194944A CN 109449486 A CN109449486 A CN 109449486A
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic 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
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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 a kind of applications of electrolysis additive, and electrolysis additive is dissolved in liquid electrolyte and forms mixed solution, and mass percentage of the electrolysis additive in the liquid electrolyte is 0.5 ~ 2%；The electrolysis additive is the mixture selected from one of carboxylic acid type organic, sulfonic acid type organic, sulfinic acid type organic, inorganic acid, thioether type organic and inorganic ceramic powder or a variety of compositions.By using micro electrolysis additive in the electrolytic solution, not only have the advantages that excellent dendritic growth inhibits, safety and reliability improves, it has been also prevented from the dissolution of positive electrode transition metal due to caused by high voltage, its cycle performance and security performance can be greatly improved, suitable for the large-scale application liquid state batteries.
Description
Technical field
The invention belongs to field of lithium, are related to a kind of additive, and in particular to a kind of application of electrolysis additive.
Background technique
Nowadays, rechargeable lithium battery is in small-sized portable electronic product facility, large-scale electric power means of transport and can
It popularizes and comes in the utilization of renewable sources of energy storage system.For universal, liquid lithium ionic cell is with nowadays occupying leading market
Position.But that there are a series of problems is urgently to be resolved for liquid lithium ionic cell.For stratiform and spinel strucutre oxides anode material
For material, anode is in high oxidation state under Charging state, is easy to happen reduction phase transformation, transition metal ions and electrolysis in skeleton
It is precipitate into electrolyte after solvent interaction in matter, and is diffused into cathode, is catalyzed the further growth of SEI film, while positive material
Material surface texture is destroyed, and internal resistance increases, reversible capacity loss.For the layered oxide of high capacity, higher electricity is being charged to
When pressure, the oxygen in positive lattice is easy to lose electronics, is precipitated in the form of free oxygen from lattice, and oxidation occurs instead with electrolyte
It answers, leads to thermal runaway, cathode material structure is also gradually destroyed.
In addition, needing to charge to high voltage in order to improve positive electrode capacity to deviate from more lithiums, being directed to cobalt at present
The electrolyte solution of sour lithium can be charged to 4.45V, and nickel ion doped can be charged to 4.90V, continue to be charged to higher voltage, electrolysis
Irreversible transition can also occur for matter meeting oxygenolysis, positive electrode surface.For lithium an- ode, the removing of lithium in charge and discharge process
Li dendrite can be generated with deposition, battery short circuit is will also result in, leads to safety issue.For other negative electrode materials, due to insertion
The slower reason of negative electrode material Internal dynamics, low temperature overcharge or large current charge under, lithium metal is directly precipitated in cathode table
Face may cause Li dendrite, cause micro-short circuit；Reduction reaction directly occurs for the lithium metal and liquid electrolyte of high activity, loses
Active lithium increases internal resistance.For sode cell, it is also faced with the problem same with lithium battery.New electrolyte function is developed to add
Adding agent is to alleviate a kind of method of liquid state batteries problem above.
Summary of the invention
A kind of application of electrolysis additive is provided the invention aims to overcome the deficiencies in the prior art.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: a kind of application of electrolysis additive, by electrolyte
Additive, which is dissolved in liquid electrolyte, forms mixed solution, quality of the electrolysis additive in the liquid electrolyte
Percentage composition is 0.5~2%；The electrolysis additive is to have selected from carboxylic acid type organic, sulfonic acid type organic, sulfinic acid class
The mixture of one of machine object, inorganic acid, thioether type organic and inorganic ceramic powder or a variety of compositions.
Optimally, the liquid electrolyte is that lithium salts or/and sodium salt are dissolved in organic solvent to be made；The lithium salts be selected from
Lithium hexafluoro phosphate, bis trifluoromethyl sulfimide lithium, dioxalic acid lithium borate, lithium perchlorate, difluorine oxalic acid boracic acid lithium, tetrafluoro boric acid
The mixture of one of lithium and trifluoromethyl sulfonic acid lithium or a variety of compositions；The sodium salt is selected from sodium perchlorate and/or double three
Methyl fluoride sulfimide sodium；The organic solvent is selected from ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate
One of ester, 1,3- dioxolanes, glycol dimethyl ether, tetraethyleneglycol dimethyl ether, diethylene glycol dimethyl ether or a variety of compositions
Mixture.
Optimally, the carboxylic acid type organic includes formic acid, acetic acid, propionic acid, butyric acid, octanoic acid, adipic acid, ethanedioic acid, third
Diacid, succinic acid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid (TPA), quinoline-3-carboxylic acid, 4-
Hydroxy cyclohexylphenyl formic acid, 1- methyl draw azoles -3- carboxylic acid and acetylenedicarboxylic acid.
Optimally, the sulfonic acid type organic include dodecyl benzene sulfonic acid, p-methyl benzenesulfonic acid, fourth sulfonic acid, Loprazolam,
NSC 209983,2- naphthalene sulfonic acids, isoquinoline-5-sulfonic acid, o-aminophenol sulfonic acid, 3- pyridine-sulfonic acid and morpholino b acid.
Optimally, the sulfinic acid type organic includes benzenesulfinic acid, perfluoroalkyl sulfinic acid and methyl sulfinate.
Optimally, the inorganic acid includes hydrochloric acid, nitric acid, boric acid, sulfuric acid, carbonic acid and phosphoric acid.
Optimally, the thioether type organic includes allyl methyl disulfide, benzyl phenyl thioether, 3,3'- dihydroxy two
Diphenyl disulfide ether, to toluene disulfide, allyl propyl thioether, two sulphur of allyl methyl sulfide, diallyl disulfide and Dithiophene.
Optimally, the inorganic ceramic powder includes Li1.5Al0.5Ge1.5P3O12、Li10GeP2S12、
Li6.4La3Zr1.4Ta0.6O12And Li6.3La3Zr1.65W0.35O12。
Due to the above technical solutions, the present invention has the following advantages over the prior art: electrolyte of the present invention adds
The application for adding agent is not only inhibited with excellent dendritic growth, peace by using micro electrolysis additive in the electrolytic solution
The advantages of full property and reliability improve, has been also prevented from the dissolution of positive electrode transition metal due to caused by high voltage, can be substantially
Its cycle performance and security performance are improved, suitable for the large-scale application liquid state batteries.
Detailed description of the invention
Fig. 1 is that the electrolyte obtained containing micro perfluoroalkyl sulfinic acid additive of embodiment 1 assembles lithium Symmetrical cells
Cyclic polarization curve.
Fig. 2 is that the electrolyte containing trace mineral supplement made from embodiment 1 is applied to the secondary electricity of LiFePO4 // lithium metal
The cycle performance figure in pond.
Fig. 3 is that the electrolyte obtained containing micro dodecyl benzene sulfonic acid additive of embodiment 5 assembles lithium Symmetrical cells
Cyclic polarization curve.
Fig. 4 is that the electrolyte obtained containing micro dodecyl benzene sulfonic acid additive of embodiment 5 is applied to ternary material
Material // lithium metal secondary cell cycle performance figure.
Fig. 5 is that the electrolyte containing allyl methyl disulfide trace mineral supplement made from embodiment 9 is applied to vanadium phosphate
Sodium // sodium metal secondary batteries cycle performance figure.
Specific embodiment
It is molten to be dissolved in formation mixing in liquid electrolyte by the application of electrolysis additive of the present invention for electrolysis additive
Liquid, mass percentage of the electrolysis additive in the liquid electrolyte are 0.5~2%；The electrolyte addition
Agent is selected from carboxylic acid type organic, sulfonic acid type organic, sulfinic acid type organic, inorganic acid, thioether type organic and inorganic pottery
The mixture of one of porcelain powder or a variety of compositions.By using micro electrolysis additive in the electrolytic solution, not only have
There is the advantages of excellent dendritic growth inhibition, safety and reliability improve, has been also prevented from positive electrode since high voltage causes
Transition metal dissolution, its cycle performance and security performance can be greatly improved, suitable for liquid state batteries on a large scale answer
With.
Lithium salts or/and sodium salt are usually dissolved in organic solvent and are made by above-mentioned liquid electrolyte using routine；Lithium
Salt be selected from lithium hexafluoro phosphate, bis trifluoromethyl sulfimide lithium, dioxalic acid lithium borate, lithium perchlorate, difluorine oxalic acid boracic acid lithium,
The mixture of one of LiBF4 and trifluoromethyl sulfonic acid lithium or a variety of compositions；Sodium salt be selected from sodium perchlorate and/or
Bis trifluoromethyl sulfimide sodium；The organic solvent is selected from ethylene carbonate, diethyl carbonate, dimethyl carbonate, carbonic acid
One of acrylic ester, 1,3- dioxolanes, glycol dimethyl ether, tetraethyleneglycol dimethyl ether, diethylene glycol dimethyl ether or a variety of groups
At mixture.Aforesaid operations carry out usually in glove box, and water oxygen value is less than 0.1ppm.
The carboxylic acid type organic includes formic acid, acetic acid, propionic acid, butyric acid, octanoic acid, adipic acid, ethanedioic acid, malonic acid, fourth
Diacid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid (TPA), quinoline-3-carboxylic acid, 4- hydroxy cyclohexylphenyl
Formic acid, 1- methyl draw azoles -3- carboxylic acid and acetylenedicarboxylic acid etc.；The sulfonic acid type organic includes dodecyl benzene sulfonic acid, to toluene
Sulfonic acid, fourth sulfonic acid, Loprazolam, NSC 209983,2- naphthalene sulfonic acids, isoquinoline-5-sulfonic acid, o-aminophenol sulfonic acid, 3- pyridine sulphur
Acid and morpholino b acid etc.；The sulfinic acid type organic includes benzenesulfinic acid, perfluoroalkyl sulfinic acid and methyl sulfinate etc..
The inorganic acid includes hydrochloric acid, nitric acid, boric acid, sulfuric acid, carbonic acid and phosphoric acid etc..The thioether type organic includes allyl methyl
Two sulphur, benzyl phenyl thioether, 3,3'- dihydroxy diphenyl disulfide, to toluene disulfide, allyl propyl thioether, allyl first
Two sulphur of thioether, diallyl disulfide and Dithiophene etc..The inorganic ceramic powder includes Li1.5Al0.5Ge1.5P3O12、
Li10GeP2S12、Li6.4La3Zr1.4Ta0.6O12And Li6.3La3Zr1.65W0.35O12Deng.
It is used for above-mentioned mixed solution to make battery as electrolyte material, which includes anode, cathode and cathode
Electrolyte material between anode；The battery be usually can repeatedly charge and discharge (such as lithium metal battery, lithium ion full battery,
Sodium metal battery etc.；And in LiFePO4 (LiFePO4), cobalt acid lithium (LiCoO2), ternary material (LiNiCoMnO2), phosphoric acid
Vanadium sodium (Na3V2(PO4)3) etc. in secondary cells).The anode of the lithium metal battery is lithium metal；The lithium ion full battery
Anode material is the mixing selected from one of manganese dioxide, graphite, active carbon, lithium titanate and silicon materials etc. or a variety of compositions
Object；And the anode of sodium metal battery is sodium metal.The cathode material of the battery includes active material selected from the following: cobalt acid lithium
(LiCoO2), LiFePO4 (LiFePO4), ternary material (LiNiCoMnO2), nickel ion doped (LiNi0.5Mn1.5O4), rich lithium layer
Shape oxide (xLi2MnO3·(1-x)LiMO2, M=Ni, Co, Mn) etc. and their combination.The yin of the sodium metal battery
Pole material includes active material selected from the following: sodium cobalt oxide (NaxCoO2), sodium manganese oxidation close (NaxMnO2), transition gold
Belong to sodium ascorbyl phosphate (NaMPO4(M=Fe, Co, Ni, Mn, V)), transition metal fluorophosphoric acid sodium salt (NaMPO4F (M=Fe, Co, Ni,
Mn, V)) etc. and their combination.It comprising conductive additive and can also be glued in the electrode material (anode or/and cathode)
Tie agent.The conductive additive is in carbon black, natural graphite, synthetic graphite, graphene, metallic particles etc. and aforementioned component
At least two combination；The binder is selected from Kynoar, polytetrafluoroethylene (PTFE), carboxymethyl cellulose etc. and aforementioned
At least two combination in component.
Below in conjunction with embodiment, invention is further explained.
Embodiment 1
The present embodiment provides a kind of application of electrolysis additive, specifically: in the glove box full of argon gas, by perfluor
Alkyl sulfinic acid is dissolved in liquid electrolyte with the concentration of 1wt% and forms uniform mixed solution；Liquid electrolyte is 1M six
Lithium fluophosphate is dissolved in ethylene carbonate/diethyl carbonate (mass ratio of ethylene carbonate and diethyl carbonate is 1:1).
Embodiment 2
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 1, unlike:
The concentration of perfluoroalkyl sulfinic acid is 0.5wt%.
Embodiment 3
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 1, unlike:
The concentration of perfluoroalkyl sulfinic acid is 2wt%.
Embodiment 4
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 1, unlike:
Specific liquid electrolyte is that 1M lithium hexafluoro phosphate is dissolved in ethylene carbonate/diethyl carbonate/dimethyl carbonate (1:1:1vol%).
Embodiment 5
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 1, unlike:
Additive is dodecyl benzene sulfonic acid.
Embodiment 6
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 5, unlike:
Dodecyl benzene sulfonic acid is dissolved in liquid electrolyte with the concentration of 0.5wt%.
Embodiment 7
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 5, unlike:
Dodecyl benzene sulfonic acid is dissolved in liquid electrolyte with the concentration of 2wt%.
Embodiment 8
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 5, unlike:
Specific liquid electrolyte is that 1M lithium hexafluoro phosphate is dissolved in ethylene carbonate/diethyl carbonate/dimethyl carbonate (1:1:1vol%)
Embodiment 9
The present embodiment provides a kind of application of electrolysis additive, specifically: in the glove box full of argon gas, by allyl
Two sulphur of ylmethyl is dissolved in liquid electrolyte with the concentration of 1wt% forms uniform mixed solution.Specifically liquid electrolyte is
1M sodium perchlorate is dissolved in ethylene carbonate/propylene carbonate (1:1vol%).
Embodiment 10
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 9, unlike:
Allyl methyl disulfide is dissolved in liquid electrolyte with the concentration of 0.5wt%.
Embodiment 11
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 9, unlike:
Dodecyl benzene sulfonic acid is dissolved in liquid electrolyte with the concentration of 2wt%.
Embodiment 12
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 9, unlike:
Specific liquid electrolyte is that 1M bis trifluoromethyl sulfimide sodium is dissolved in tetraethyleneglycol dimethyl ether.
Embodiment 13
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 9, unlike:
Additive is two sulphur of Dithiophene.
Embodiment 14
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 1, unlike:
Additive is quinoline-3-carboxylic acid.
Embodiment 15
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 1, unlike:
Additive is terephthalic acid (TPA).
Embodiment 16
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 1, unlike:
Additive is to toluene disulfide.
Embodiment 17
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 1, unlike:
Additive is phosphoric acid.
Embodiment 18
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 1, unlike:
Additive is Li10GeP2S12。
Embodiment 19
The present embodiment provides a kind of application of electrolysis additive, it with it is almost the same in embodiment 1, unlike:
Additive is Li1.5Al0.5Ge1.5P3O12。
Experimental example 1
By LiFePO4 (LiFePO4) material: acetylene black: PVDF is dispersed in N-Methyl pyrrolidone in the ratio of 8:1:1
(NMP) it is uniformly dispersed in and slurry is made, scratch on aluminium foil, it is the disk of 12mm as cell positive pole that diameter is cut into after dry
Piece；The activity substance content of single pole piece is averagely about 3.0mg/cm2.Contain micro electricity using prepared in Examples 1 to 4
The liquid electrolyte of solution solution additive dresses up LiFePO4 (LiFePO4The chemical property of battery is carried out after) // lithium metal battery
Test.Test result is shown in Table 1.
Electrochemical property test performance table of the table 1 based on liquid electrolyte in Examples 1 to 4
| Initial capacity | Circulating ring number | Recycle conservation rate | |
| Embodiment 1 | 141 | 250 | 93% |
| Embodiment 2 | 142 | 200 | 75% |
| Embodiment 3 | 139 | 200 | 83% |
| Embodiment 4 | 140 | 250 | 94% |
Experimental example 2
By ternary material (LiNiCoMnO2) material: acetylene black: PVDF is dispersed in N- crassitude in the ratio of 8:1:1
It is uniformly dispersed in ketone (NMP) and slurry is made, scratch on aluminium foil, it is the disk of 12mm as anode that diameter is cut into after dry
Pole piece.The activity substance content of single pole piece is averagely about 3.0mg/cm2.Using prepared containing micro in embodiment 5~8
The liquid electrolyte of electrolysis additive dresses up ternary material (LiNiCoMnO2The electrification of battery is carried out after) // lithium metal battery
Learn performance test.Test result is shown in Table 2.
Electrochemical property test performance table of the table 2 based on liquid electrolyte in embodiment 5~8
| Initial capacity | Circulating ring number | Recycle conservation rate | |
| Embodiment 5 | 136 | 200 | 99% |
| Embodiment 6 | 137 | 200 | 50% |
| Embodiment 7 | 134 | 200 | 81% |
| Embodiment 8 | 137 | 200 | 98% |
Experimental example 3
By vanadium phosphate sodium (Na3V2(PO4)3) material: acetylene black: PVDF is dispersed in N- crassitude in the ratio of 8:1:1
It is uniformly dispersed in ketone (NMP) and slurry is made, scratch on aluminium foil, it is the disk of 12mm as anode that diameter is cut into after dry
Pole piece.The activity substance content of single pole piece is averagely about 3.0mg/cm2.Using prepared containing micro- in embodiment 9~13
The liquid electrolyte of amount electrolysis additive dresses up vanadium phosphate sodium (Na3V2(PO4)3The electricity of battery is carried out after) // sodium metal battery
Chemical property test.Test result is shown in Table 3.
Electrochemical property test performance table of the table 3 based on liquid electrolyte in embodiment 9~13
| Initial capacity | Circulating ring number | Recycle conservation rate | |
| Embodiment 9 | 96 | 200 | 84% |
| Embodiment 10 | 97 | 100 | 40% |
| Embodiment 11 | 94 | 150 | 70% |
| Embodiment 12 | 95 | 200 | 83% |
| Embodiment 13 | 93 | 200 | 75% |
Fig. 1 is that the electrolyte obtained containing micro perfluoroalkyl sulfinic acid additive of embodiment 1 assembles lithium Symmetrical cells
Cyclic polarization curve, from figure 1 it appears that the Symmetrical cells are in lithium deposition/stripping process as time/period generates electricity
Pressure fluctuation is more gentle, keeps the polarization potential of very little to compare with additive-free Symmetrical cells and shows excellent stability.Figure
2 are applied to LiFePO4 // lithium metal secondary cell cyclicity for the electrolyte containing trace mineral supplement made from embodiment 1
It can scheme, it can be seen that microelectrolysis solution additive of the invention can maintain LiFePO4 // lithium metal secondary cell stabilization to follow
Ring.Fig. 3 is that the electrolyte obtained containing micro dodecyl benzene sulfonic acid additive of embodiment 5 assembles lithium Symmetrical cells circulation pole
Change curve, it can be seen that the Symmetrical cells keep the polarization potential of very little and additive-free in lithium deposition/stripping process
Symmetrical cells are compared and show excellent stability.Fig. 4, which is that embodiment 5 is obtained, contains micro dodecyl benzene sulfonic acid additive
Electrolyte be applied to ternary material // lithium metal secondary cell cycle performance figure, it can be seen that microelectrolysis liquid of the invention
Additive can maintain ternary material // lithium metal secondary cell to stablize circulation.Fig. 5 is to contain allyl made from embodiment 9
The electrolyte of two sulphur trace mineral supplement of methyl is applied to vanadium phosphate sodium // sodium metal secondary batteries cycle performance figure, also shows
Outstanding cycle performance shows that microelectrolysis solution additive of the invention is equally applicable to sode cell.
In conclusion not only there is microelectrolysis solution additive provided by the invention excellent dendritic growth to inhibit, safety
Property and reliability improve the advantages of, be also prevented from the dissolution of positive electrode transition metal due to caused by high voltage, can substantially mention
Its high cycle performance and security performance, suitable for large-scale application liquid state batteries, including lithium battery, sode cell etc..
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of application of electrolysis additive, it is characterised in that: electrolysis additive is dissolved in liquid electrolyte and is formed
Mixed solution, mass percentage of the electrolysis additive in the liquid electrolyte are 0.5 ~ 2%；The electrolyte
Additive is selected from carboxylic acid type organic, sulfonic acid type organic, sulfinic acid type organic, inorganic acid, thioether type organic and nothing
The mixture of one of machine ceramic powders or a variety of compositions.
2. the application of electrolysis additive according to claim 1, it is characterised in that: the liquid electrolyte is by lithium salts
Or/and sodium salt is dissolved in organic solvent and is made；The lithium salts is selected from lithium hexafluoro phosphate, bis trifluoromethyl sulfimide lithium, two grass
One of sour lithium borate, lithium perchlorate, difluorine oxalic acid boracic acid lithium, LiBF4 and trifluoromethyl sulfonic acid lithium or a variety of compositions
Mixture；The sodium salt is selected from sodium perchlorate and/or bis trifluoromethyl sulfimide sodium；The organic solvent is selected from carbon
Vinyl acetate, diethyl carbonate, dimethyl carbonate, propene carbonate, 1,3- dioxolanes, glycol dimethyl ether, tetraethylene glycol
The mixture of one of dimethyl ether, diethylene glycol dimethyl ether or a variety of compositions.
3. the application of electrolysis additive according to claim 1, it is characterised in that: the carboxylic acid type organic includes first
Acid, acetic acid, propionic acid, butyric acid, octanoic acid, adipic acid, ethanedioic acid, malonic acid, succinic acid, maleic acid, tartaric acid, benzoic acid, benzene second
Acid, phthalic acid, terephthalic acid (TPA), quinoline-3-carboxylic acid, 4- hydroxy cyclohexylphenyl formic acid, 1- methyl draw azoles -3- carboxylic acid and butine two
Acid.
4. the application of electrolysis additive according to claim 1, it is characterised in that: the sulfonic acid type organic includes ten
Dialkyl benzene sulfonic acids, p-methyl benzenesulfonic acid, fourth sulfonic acid, Loprazolam, NSC 209983,2- naphthalene sulfonic acids, isoquinoline-5-sulfonic acid, neighbour
Amino phenol sulfonic acid, 3- pyridine-sulfonic acid and morpholino b acid.
5. the application of electrolysis additive according to claim 1, it is characterised in that: the sulfinic acid type organic includes
Benzenesulfinic acid, perfluoroalkyl sulfinic acid and methyl sulfinate.
6. the application of electrolysis additive according to claim 1, it is characterised in that: the inorganic acid includes hydrochloric acid, nitre
Acid, boric acid, sulfuric acid, carbonic acid and phosphoric acid.
7. the application of electrolysis additive according to claim 1, it is characterised in that: the thioether type organic includes alkene
Two sulphur of hydroxypropyl methyl, benzyl phenyl thioether, 3,3'- dihydroxy diphenyl disulfide, to toluene disulfide, allyl propyl thioether,
Two sulphur of allyl methyl sulfide, diallyl disulfide and Dithiophene.
8. the application of electrolysis additive according to claim 1, it is characterised in that: the inorganic ceramic powder includes
Li1.5Al0.5Ge1.5P3O12、Li10GeP2S12、Li6.4La3Zr1.4Ta0.6O12And Li6.3La3Zr1.65W0.35O12。
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