CN107068971A - A kind of lithium anode of lithium battery - Google Patents
A kind of lithium anode of lithium battery Download PDFInfo
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- CN107068971A CN107068971A CN201611129703.XA CN201611129703A CN107068971A CN 107068971 A CN107068971 A CN 107068971A CN 201611129703 A CN201611129703 A CN 201611129703A CN 107068971 A CN107068971 A CN 107068971A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a kind of lithium anode of lithium battery, one layer of solid electrolyte protective layer is contained on the lithium anode surface.The present invention introduces floor height effect, stable solid electrolyte interface film on lithium piece surface by carrying out electrochemical pre-treatment to cathode of lithium；During lithium ion is deposited and deviate from repeatedly, on the one hand the solid electrolyte protective layer with the appearance of dendrite inhibition, can improve the security performance of battery, on the other hand can also completely cut off electrolyte and lithium metal, protect lithium metal from the corrosion of electrolyte；By the screening of electroplating technology and Arrays Aluminum Films in Acid Solution, effective protection of lithium anode is realized, the cycle life of lithium metal battery is improved.Compared to the cathode of lithium without processing; the lithium anode protected by solid-state electrolyte layer can effective dendrite inhibition shape lithium deposit appearance; reduce the side reaction of electrolyte and lithium metal; the cycle efficieny and cyclical stability of battery are improved, so as to improve the cycle life using lithium metal as the lithium metal battery of negative pole.
Description
Technical field
The present invention relates to a kind of lithium anode, belong to the lithium metal battery technical field using lithium metal as negative pole.
Background technology
The life of the energy and the people are closely bound up, and the appearance of battery allow the energy utilization more conveniently and quickly.Previous generation
Discipline the nineties, Sony develop can safe utilization graphite cathode, bring lithium ion battery in personal electronic equipments
Deng the sizable application in field.But, with the increase in demand of high-end electronic devices and electric automobile, based on conventional oxide positive pole
Gradually it is difficult to meet demand with the lithium ion battery of graphite cathode, the energy-storage system of development higher energy density has been compeled in eyebrow
Eyelash.In known electrodes material, lithium an- ode is with 3860mAhg-1High power capacity and most negative potential (- 3.040V vs. are marked
Quasi- hydrogen electrode) and " Holy grail " as energy storage circle, paid close attention to by researcher (Energy Environ.Sci.2014,7,
513).The empty battery (3500Wh/kg) of lithium-sulfur cell (2600Wh/kg) and lithium by negative pole of lithium metal is close with its high energy
Degree, and it is considered as the important selection of energy-storage battery of future generation.
Lithium metal battery is with the obvious advantage, but the problem of but encounter negative pole dendritic growth in actual applications.Work as metal
When lithium is as secondary battery negative pole, the reversible deposition of lithium metal causes dendritic growth.Dendrite pierces through barrier film, causes battery short circuit, holds
Easily bring security incident.Dendrite inhibition growth is to realize high-energy-density lithium metal battery (such as lithium-sulfur cell, lithium-oxygen battery)
The key of sizable application.In order to which dendrite inhibition grows, security, utilization rate and the cycle life of lithium metal battery are improved, in mistake
In the half a century gone, scientist proposes a variety of solutions.Lynden professors A.Archer are added using LiF as electrolyte
Plus agent (Nature Materials 2014,13,961).Lithium ion can be big on the surface on LiF surfaces and diffusion energy is small so that lithium
Ion is easier to diffuse into uniform lithium ion around LiF, so as to realize being uniformly distributed for lithium ion.Lu etc. is by copper nano-wire
As the collector of lithium metal, the current density of negative pole can be reduced, so that extend Sand ' s time, dendrite inhibition growth
(Nano Letters 2016,16,4431).Zhao Chenzi etc. is real using the combined electrolysis solution additive of polysulfide and lithium nitrate
The stability of negative terminal surface solid electrolyte interface film is showed, so that the growth of dendrite inhibition, the security performance for improving battery is (public
The number of opening：CN 201610252402).These methods provide the new approaches of many dendrite inhibitions, but in application process but by
The limitation of many conditions, such as certain additive can be only applied in certain specific solvent, three-dimensional manometer skeleton can bring compared with
Many side reactions etc..How to be oriented transformation to lithium metal, obtain can dendrite inhibition growth, can be applicable to a variety of electrolysis
The lithium an- ode of liquid and battery system will have huge meaning.Therefore current lithium piece is handled, can possessed
The ability of dendrite inhibition growth, it will realize application of the same lithium piece in different batteries and electrolyte system, is realized with metal
Lithium is the practical application of the lithium metal battery of negative pole.
The content of the invention
It is an object of the invention to change the problem of current lithium metal battery negative pole cycle life is low, by conventional lithium
Piece negative pole carries out electrochemical pre-treatment, one layer of efficient solid electrolyte interface film is introduced on lithium piece surface, so as to suppress metal
The dendritic growth of cathode of lithium, reduces the side reaction of electrolyte and lithium metal, improves the utilization rate and cycle life of battery.
The technical scheme is that：A kind of lithium anode of lithium battery, it is characterised in that：The lithium anode surface
Containing one layer of solid electrolyte protective layer, the solid electrolyte protective layer is prepared using following electro-plating method：
1) prepare the mixed solution of lithium salts and organic solvent as electrolyte solution, the molar concentration of its lithium salts for 0.1~
10mol/L；
2) lithium piece is immersed in the electrolyte solution and electroplated, the electric current of electroplating process is 1 μ A cm-2~100mA
cm-2, after after lithium piece electroplating surface last layer solid electrolyte diaphragm, lithium piece is taken out, i.e., as lithium anode.
In above-mentioned technical proposal, described electrolyte solution also contains additive, and the additive is lithium nitrate, many vulcanizations
Lithium, lithium carbonate, fluorinated ethylene carbonate, vinylene carbonate, propylene sulfite, ethylene sulfite, lithium halide, titanium dioxide
One or more in sulphur and carbon dioxide, the concentration of additive is in 0.001~1mol L-1。
In above-mentioned technical proposal, the lithium salts is lithium hexafluoro phosphate, hexafluoro lithium borate, hexafluoroarsenate lithium, lithium perchlorate, double
The yellow imide li of ethanedioic acid lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine and two (trimethyl fluoride sulfonyl) lithiums it is one or more of
Combination.
In above-mentioned technical proposal, described organic solvent is ethylene carbonate, propene carbonate, dimethyl sulfoxide (DMSO), diformazan
Base carbonic ester, diethyl carbonate, the first and second base carbonic esters, dimethoxy-ethane, ethyl acetate, acrylonitrile, methyl formate, methyl
One or more in acrylate, tetrahydrofuran, sulfolane, 1,3- dioxolanes and tetraethyleneglycol dimethyl ether.
The described electroplating processes time is 1s~1000h, and number of processes is 1-1000 times.Electroplate the lithium piece surface of acquisition
The thickness of solid electrolyte diaphragm is 2nm~200um.
The present invention compared with prior art, has the following advantages that and high-lighting effect：The present invention is using electric plating method to lithium
The compact Chemical Pretreatment of piece, makes lithium electrode surface contain one layer of stable solid electrolyte protective layer, not only method simple possible,
And can effectively suppress the dendritic growth of lithium anode, the side reaction of electrolyte and lithium metal is reduced, battery is significantly improved
Utilization rate and cycle life；Experimental study shows that the lithium anode does not have dendrite appearance in the circulation of 10~8000 primary cells；
The lithium anode can improve the utilization rate of the cathode of lithium battery to 80~99.9999%.
Embodiment：
Contain one layer of solid electrolyte in a kind of lithium anode for lithium battery that the present invention is provided, the lithium anode surface
Protective layer, the solid electrolyte protective layer is prepared using electro-plating method.Electrolyte solution for plating is comprising certain density
Lithium salts and organic solvent.Lithium salts is lithium hexafluoro phosphate, hexafluoro lithium borate, hexafluoroarsenate lithium, lithium perchlorate, double ethanedioic acid boric acid
The one or more of the yellow imide li of lithium, difluorine oxalic acid boracic acid lithium, double fluorine and two (trimethyl fluoride sulfonyl) lithiums, lithium salts molar concentration
General is being 0.1~10mol L-1Between.Organic solvent uses ethylene carbonate, propene carbonate, dimethyl sulfoxide (DMSO), dimethyl
Carbonic ester, diethyl carbonate, the first and second base carbonic esters, dimethoxy-ethane, ethyl acetate, acrylonitrile, methyl formate, methyl-prop
One or more in olefin(e) acid ester, tetrahydrofuran, sulfolane, 1,3- dioxolanes and tetraethyleneglycol dimethyl ether.The electrolyte is molten
Liquid can also contain additive, and additive is lithium nitrate, many lithium sulfides, lithium carbonate, fluorinated ethylene carbonate, vinylene carbonate
One or more in ester, propylene sulfite, ethylene sulfite, lithium halide, sulfur dioxide, carbon dioxide etc., its mole
Concentration is 0.001~1mol L-1.The electric current of electroplating process is generally 1 μ A cm-2~100mA cm-2, processing time be 1s~
1000h, number of processes is 1-1000 times, and the thickness for electroplating the solid electrolyte diaphragm on the lithium piece surface obtained is preferably 2nm
~200um.
The present invention is further appreciated that from following examples, but the present invention is not limited solely to following examples.
Embodiment 1：Lithium piece is placed in electrolytic cell, the electrolyte used is two (trimethyl fluoride sulfonyl) lithium (2mol L-1)-
Lithium nitrate (0.001mol L-1)-DOX/dimethoxy-ethane, is electroplated 1 time, and current density is 1 μ A cm-2, the time
For 1000h, the protection film thickness obtained on lithium piece surface is 200um, and lithium piece is taken out, and lithium sulphur electricity is assembled into together with sulphur positive pole
Pond, finds, the coulombic efficiency of lithium-sulfur cell can reach 99%, and cycle life can reach 5000 circles by test.
Embodiment 2：Lithium piece is placed in electrolytic cell, the electrolyte used is biethyl diacid lithium borate (0.1mol L-1)-fluorine
For ethylene carbonate (0.01mol L-1)-ethylene carbonate/diethyl carbonate, is electroplated 50 times, and current density is 4mA cm-2,
Time is 10h, and the protection film thickness obtained on lithium piece surface is 100um, and lithium piece is taken out, and the empty battery of lithium is assembled into, by surveying
Examination finds that the coulombic efficiency of lithium sky battery can reach 92%, and cycle life can reach 500 circles.
Embodiment 3：Lithium piece is placed in electrolytic cell, the electrolyte used is yellow imide li (the 5mol L of double fluorine-1)-carbonic acid
Vinylene (0.1mol L-1)-dimethyl sulfoxide (DMSO), is electroplated 100 times, and current density is 100mA cm-2, the time is 1s, in lithium piece
The protection film thickness that surface is obtained is 50um, and lithium piece is taken out, battery is assembled into together with ternary material, is found by test,
The coulombic efficiency of the battery can reach 80%, and cycle life can reach 100 circles.
Embodiment 4：Lithium piece is placed in electrolytic cell, the electrolyte used is lithium hexafluoro phosphate (1mol L-1)-many lithium sulfides
(0.5mol L-1)-tetraethyleneglycol dimethyl ether, is electroplated 20 times, and current density is 0.5mA cm-2, the time is 0.5h, in lithium piece table
The protection film thickness that face is obtained is 10um, and lithium piece is taken out, battery is assembled into together with cobalt acid lithium, is found by test, the electricity
The coulombic efficiency in pond can reach 99.9999%, and cycle life can reach 2000 circles.
Embodiment 5：Lithium piece is placed in electrolytic cell, the electrolyte used is lithium perchlorate (0.1mol L-1)-propylene carbonate
Ester, is electroplated 800 times, and current density is 0.2mA cm-2, the time is 1h, and the protection film thickness obtained on lithium piece surface is 5um, will
Lithium piece is taken out, and battery is assembled into together with LiFePO4, is found by test, and the coulombic efficiency of the battery can reach 90%,
Cycle life can reach 5000 circles.
Embodiment 6：Lithium piece is placed in electrolytic cell, the electrolyte used is hexafluoroarsenate lithium (2.5mol L-1)-tetrahydrochysene furan
Mutter, electroplate 10 times, current density is 8mA cm-2, the time is 30s, and the protection film thickness obtained on lithium piece surface is 1um, by lithium
Piece is taken out, and battery is assembled into together with sulfur dioxide, is found by test, and the coulombic efficiency of the battery can reach 82%, follow
The ring life-span can reach 150 circles.
Embodiment 7：Lithium piece is placed in electrolytic cell, the electrolyte used is difluorine oxalic acid boracic acid lithium (2.5mol L-1)-sub-
Sulfuric acid propylene (1mol L-1The base carbonic ester of)-ethylene carbonate/diethyl carbonate/first and second, is electroplated 400 times, and current density is
100μA cm-2, the time is 30s, and the protection film thickness obtained on lithium piece surface is 20um, lithium piece is taken out, together with LiMn2O4
Battery is assembled into, is found by test, the coulombic efficiency of the battery can reach 99.5%, and cycle life can reach 1500
Circle.
Embodiment 8：Lithium piece is placed in electrolytic cell, the electrolyte used is biethyl diacid lithium borate (0.1mol L-1)-fluorine
For ethylene carbonate (0.5mol L-1)-dimethyl carbonate/diethyl carbonate, is electroplated 50 times, and current density is 40mA cm-2, the time is 10h, and the protection film thickness obtained on lithium piece surface is 500nm, and lithium piece is taken out, and is assembled into the empty battery of lithium, passes through
Test finds that the coulombic efficiency of lithium sky battery can reach 92%, and cycle life can reach 500 circles.
Embodiment 9：Lithium piece is placed in electrolytic cell, the electrolyte used is biethyl diacid lithium borate (0.1mol L-1)-carbon
Vinyl acetate/ethyl acetate, is electroplated 50 times, and current density is 0.1mA cm-2, the time is 10h, the protection obtained on lithium piece surface
Film thickness is 100nm, and lithium piece is taken out, and is assembled into the empty battery of lithium, is found by test, and the coulombic efficiency of lithium sky battery can reach
To 97%, cycle life can reach 500 circles.
Embodiment 10：Lithium piece is placed in electrolytic cell, the electrolyte used is lithium perchlorate (0.1mol L-1)-acrylonitrile,
Plating 800 times, current density is 5mA cm-2, the time is 1h, and the protection film thickness obtained on lithium piece surface is 50nm, by lithium piece
Take out, battery is assembled into together with LiFePO4, found by test, the coulombic efficiency of the battery can reach 85%, circulation
Life-span can reach 5000 circles.
Embodiment 11：Lithium piece is placed in electrolytic cell, the electrolyte used is lithium hexafluoro phosphate (2.5mol L-1)-formic acid
Methyl esters, is electroplated 10 times, and current density is 8A cm-2, the time is 30s, and the protection film thickness obtained on lithium piece surface is 10nm, will
Lithium piece is taken out, and battery is assembled into together with sulfur dioxide, is found by test, and the coulombic efficiency of the battery can reach 82%,
Cycle life can reach 150 circles.
Embodiment 12：Lithium piece is placed in electrolytic cell, the electrolyte used is lithium hexafluoro phosphate (1mol L-1)-methyl-prop
Olefin(e) acid ester, is electroplated 20 times, and current density is 0.5A cm-2, the time is 0.5h, and the protection film thickness obtained on lithium piece surface is
5nm, lithium piece is taken out, and battery is assembled into together with cobalt acid lithium, is found by test, and the coulombic efficiency of the battery can reach
99.996%, cycle life can reach 2000 circles.
Embodiment 13：Lithium piece is placed in electrolytic cell, the electrolyte used is biethyl diacid lithium borate (2.5mol L-1)-
Sulfolane, is electroplated 10 times, and current density is 3mA cm-2, the time is 30s, and the protection film thickness obtained on lithium piece surface is 2nm,
Lithium piece is taken out, battery is assembled into together with sulfur dioxide, is found by test, the coulombic efficiency of the battery can reach
82%, cycle life can reach 150 circles.
Embodiment 14：Lithium piece is placed in electrolytic cell, the electrolyte used is hexafluoro lithium borate (0.1mol L-1)-fluoro
Ethylene carbonate (0.005mol L-1)-dimethyl carbonate/diethyl carbonate, is electroplated 50 times, and current density is 4mA cm-2, the time is 10h, and the protection film thickness obtained on lithium piece surface is 20nm, and lithium piece is taken out, and the empty battery of lithium is assembled into, by surveying
Examination finds that the coulombic efficiency of lithium sky battery can reach 92%, and cycle life can reach 500 circles.
Embodiment 15：Lithium piece is placed in electrolytic cell, the electrolyte used is two (trimethyl fluoride sulfonyl) lithium (2mol L-1)-lithium carbonate (0.05mol L-1)-DOX/dimethoxy-ethane, is electroplated 1000 times, and current density is 40 μ A cm-2, the time is 1h, and the protection film thickness obtained on lithium piece surface is 60nm, and lithium piece is taken out, lithium sulphur is assembled into together with sulphur positive pole
Battery, finds, the coulombic efficiency of lithium-sulfur cell can reach 99%, and cycle life can reach 5000 circles by test.
Embodiment 16：Lithium piece is placed in electrolytic cell, the electrolyte used is difluorine oxalic acid boracic acid lithium (2.5mol L-1)-
Ethylene sulfite (0.5mol L-1)-ethylene carbonate, is electroplated 400 times, and current density is 10mA cm-2, the time is 15min,
The protection film thickness obtained on lithium piece surface is 200nm, and lithium piece is taken out, battery is assembled into together with LiMn2O4, by test
It was found that, the coulombic efficiency of the battery can reach 99.9%, and cycle life can reach 1500 circles.
Embodiment 17：Lithium piece is placed in electrolytic cell, the electrolyte used is two (trimethyl fluoride sulfonyl) lithium (2mol L-1)-lithium fluoride (0.8mol L-1)-DOX/dimethoxy-ethane, is electroplated 300 times, and current density is 300 μ A cm-2, the time is 10h, and the protection film thickness obtained on lithium piece surface is 800nm, and lithium piece is taken out, lithium is assembled into together with sulphur positive pole
Sulphur battery, finds, the coulombic efficiency of lithium-sulfur cell can reach 99.91%, and cycle life can reach 5000 circles by test.
Embodiment 18：Lithium piece is placed in electrolytic cell, the electrolyte used is yellow imide li (the 5mol L of double fluorine-1)-carbon
Sour vinylene, and sulfur dioxide is poured into electrolytic cell, electroplate 10 times, current density is 0.1mA cm-2, the time is 5h,
The protection film thickness that lithium piece surface is obtained is 50nm, and lithium piece is taken out, battery is assembled into together with ternary material, is sent out by test
Existing, the coulombic efficiency of the battery can reach 80%, and cycle life can reach 100 circles.
Embodiment 19：Lithium piece is placed in electrolytic cell, the electrolyte used is two (trimethyl fluoride sulfonyl) lithium (1mol L-1)-ethylene carbonate/ethyl acetate, and sulfur dioxide is poured into electrolytic cell, electroplate 50 times, current density is 40mA cm-2,
Time is 10s, and the protection film thickness obtained on lithium piece surface is 40 μm, and lithium piece is taken out, battery is assembled into together with sulphur positive pole,
Found by test, the coulombic efficiency of the battery can reach 99.95%, and cycle life can reach 10 circles.
Embodiment 20：Lithium piece is placed in electrolytic cell, the electrolyte used is yellow imide li (the 4mol L of double fluorine-1)-1,
3- dioxolanes/dimethoxy-ethane, and carbon dioxide is poured into electrolytic cell, electroplate 2 times, current density is 0.8mA cm-2,
Time is 4.5h, and the protection film thickness obtained on lithium piece surface is 15 μm, and lithium piece is taken out, electricity is assembled into together with LiFePO4
Pond, finds, the coulombic efficiency of the battery can reach 89.9%, and cycle life can reach 8000 circles by test.
Claims (6)
1. a kind of lithium anode of lithium battery, it is characterised in that：Contain one layer of solid state electrolysis quality guarantee in the lithium anode surface
Sheath, the solid electrolyte protective layer is prepared using following electro-plating method：
1) prepare the mixed solution of lithium salts and organic solvent as electrolyte solution, the molar concentration of its lithium salts for 0.1~
10mol/L；
2) lithium piece is immersed in the electrolyte solution and electroplated, the electric current of electroplating process is 1 μ A cm-2~100mA cm-2,
After after lithium piece electroplating surface last layer solid electrolyte diaphragm, lithium piece is taken out, i.e., as lithium anode.
2. according to a kind of lithium anode of lithium battery described in claim 1, it is characterised in that：Described electrolyte solution contains
There is additive, the additive is lithium nitrate, many lithium sulfides, lithium carbonate, fluorinated ethylene carbonate, vinylene carbonate, sulfurous acid
One or more in propylene, ethylene sulfite, lithium halide, sulfur dioxide and carbon dioxide, the molar concentration of additive
In 0.001~1molL-1。
3. a kind of lithium anode of lithium battery according to claim 1, it is characterised in that：The lithium salts is hexafluorophosphoric acid
The yellow acid imide of lithium, hexafluoro lithium borate, hexafluoroarsenate lithium, lithium perchlorate, biethyl diacid lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine
One or more of combinations in lithium and two (trimethyl fluoride sulfonyl) lithiums.
4. a kind of lithium anode of lithium battery according to claim 1, it is characterised in that:Described organic solvent is carbon
Vinyl acetate, propene carbonate, dimethyl sulfoxide (DMSO), dimethyl carbonate, diethyl carbonate, the first and second base carbonic esters, dimethoxy
Base ethane, ethyl acetate, acrylonitrile, methyl formate, methacrylate, tetrahydrofuran, sulfolane, 1,3- dioxolanes and four
One or more of combinations in glycol dimethyl ether.
5. according to a kind of lithium anode of lithium battery described in claim 1-4 any claims, it is characterised in that：Plating
Processing time is 1s~1000h, and number of processes is 1-1000 times.
6. according to a kind of lithium anode of lithium battery described in claim 1-4 any claims, it is characterised in that：Plating
The thickness of the solid electrolyte diaphragm on the lithium piece surface of acquisition is 2nm~200um.
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| CN201611129703.XA CN107068971A (en) | 2016-12-09 | 2016-12-09 | A kind of lithium anode of lithium battery |
| PCT/CN2017/113586 WO2018103563A1 (en) | 2016-12-09 | 2017-11-29 | Lithium metal negative electrode utilized in lithium battery |
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| CN201611129703.XA CN107068971A (en) | 2016-12-09 | 2016-12-09 | A kind of lithium anode of lithium battery |
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