CN106876708B - A kind of metal sulfide is applied to the method for cathode plate for lithium secondary battery - Google Patents
A kind of metal sulfide is applied to the method for cathode plate for lithium secondary battery Download PDFInfo
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- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 11
- -1 metals sulfide Chemical class 0.000 claims abstract description 6
- 239000007772 electrode material Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 24
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 150000002170 ethers Chemical class 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- 230000002441 reversible effect Effects 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 239000005486 organic electrolyte Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 125000006091 1,3-dioxolane group Chemical class 0.000 claims description 2
- PLUBXMRUUVWRLT-UHFFFAOYSA-N Ethyl methanesulfonate Chemical compound CCOS(C)(=O)=O PLUBXMRUUVWRLT-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 229910016323 MxSy Inorganic materials 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical group COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- LZOZLBFZGFLFBV-UHFFFAOYSA-N sulfene Chemical compound C=S(=O)=O LZOZLBFZGFLFBV-UHFFFAOYSA-N 0.000 claims 1
- 238000002347 injection Methods 0.000 abstract description 6
- 239000007924 injection Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 29
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 22
- 229910052750 molybdenum Inorganic materials 0.000 description 22
- 239000011733 molybdenum Substances 0.000 description 22
- 238000004073 vulcanization Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 230000004913 activation Effects 0.000 description 6
- 230000002427 irreversible effect Effects 0.000 description 6
- 150000002632 lipids Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000002482 conductive additive Substances 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of methods that metal sulfide is applied to cathode plate for lithium secondary battery, belong to electrochemical technology field.The present invention, come Effective Regulation metal sulfide electrode material, makes it in 1.7V~3.1V (vs.Li/Li by electrochemical charge injection process+) have and stablize electro-chemical activity, it can be used as positive electrode for lithium secondary battery.The present invention is suitable for various metals sulfide.Present invention process process is simple and compatible with prior art simultaneously, can effectively simplify production, the matching process of electrode material, therefore has great application prospect.
Description
Technical field:
The present invention relates to electrochemical technology fields, and in particular to a kind of metal sulfide is applied to cathode plate for lithium secondary battery
Method.
Background technique:
Metal sulfide can change reaction, form nano-metal particle and lithium sulfide Due to reaction lithium storage content with higher (500-1200mAh/g), lower potential plateau (<
1.5V(vs.Li/Li+)), it is considered to be one of ideal lithium ion battery negative material is widely studied in recent years.
At present metal sulfide as negative electrode of lithium ion battery there are poor circulation, coulombic efficiency is low the problems such as, it is practical
It is challenged using still suffering from.Firstly, metal sulfide and its product lithium sulfide poorly conductive, cause conversion reaction to have poor
Dynamic conditions and invertibity, it is metal sulfide that part reaction product, which is difficult to reversible transformation during the charging process,；Secondly, metal
Sulfide volume change in charge and discharge process is larger, and electrode is caused to generate dusting and irreversible side reaction generation (charge and discharge
In the process, newly generated electrode surface is reacted with electrolyte generates SEI film)；Third metal sulfide pole in charge and discharge process
Change (charge and discharge platform is not overlapped) is larger, causes energy efficiency lower.
The compound of the however reaction product of metal sulfide --- lithium sulfide and metal nanoparticle can be used as secondary
Cell positive material: wherein lithium sulfide can be used as active material, and reversible electrochemical reaction occurs: Its
Current potential 2.4V (vs.Li/Li+), specific capacity (1163mAh/g) with higher；Meanwhile vulcanization also can be improved in metal nanoparticle
The electric conductivity of lithium.Based on this, researcher wishes to metal sulfide being applied to cathode plate for lithium secondary battery.
Summary of the invention:
The purpose of the present invention is to provide a kind of methods that metal sulfide is applied to cathode plate for lithium secondary battery, by " swashing
The positive-active of work " shift reaction product lithium sulfide realizes application of the metal sulfide as cathode plate for lithium secondary battery.
To achieve the above object, the technical solution adopted in the present invention is as follows:
A kind of metal sulfide is applied to the method for cathode plate for lithium secondary battery, it is characterised in that: this method includes following step
It is rapid:
(1) using metal sulfide as active electrode material, it is prepared into metal sulfide electrode；
(2) by electrochemical charge inject method prepared metal sulfide electrode is regulated and controled, make its
1.7V~3.1V (vs.Li/Li+) with after electro-chemical activity, that is, obtain the cathode plate for lithium secondary battery.
In above-mentioned steps (1), the metal sulfide is in molybdenum sulfide, cobalt sulfide, iron sulfide, copper sulfide and nickel sulfide etc.
One or more it is compound.The manufacture craft of metal sulfide electrode be common process, it may be assumed that by metal sulfide, binder and
Conductive agent successively carries out ingredient, coating, tabletting and slice and obtains.
In above-mentioned steps (2), prepared metal sulfide electrode is adjusted by the method that electrochemical charge injects
The detailed process of control are as follows: using the metal sulfide electrode of step (1) preparation as working electrode, lithium piece is used as to electrode and reference
Electrode, while electrolyte is added, it is injected by electrochemical charge, to realize the regulation to the electro-chemical activity of metal sulfide.
Injecting the regulation active process of metal sulfide by electrochemical charge is to carry out electricity by control blanking voltage
The adjustment of pole electro-chemical activity；Detailed process are as follows: make electrode in potential region 0.01V~1.4V (vs.Li/Li first+) constant current
Charge and discharge are primary, and change reactionUtilize metal sulfide conversion reaction
Poorly reversible feature, acquisition can not reversion products --- transition metal nanoparticles M and lithium sulfide (Li2S)；Then regulation electrode
Current potential reaches 3.1V (vs.Li/Li+), " activation " irreversible product lithium sulfideFinally in positive section
1.7V~3.1V (vs.Li/Li+) constant current charge-discharge circulation is carried out, so that obtaining has the metal vulcanization for stablizing electro-chemical activity
Object anode, i.e. cathode plate for lithium secondary battery.
In step (2), after carrying out electrochemical regulating and controlling processing to prepared metal sulfide electrode, gained lithium secondary battery
Anode is in potential region 1.7V~3.1V (vs.Li/Li+) react in charge and discharge process.
In step (2), the electrolyte is organic electrolyte (such as perchlorate, tetrafluoroborate, double fluoroform sulphonyl
The solution in organic solvent such as imine lithium, hexafluorophosphate or trifluoromethyl sulfonic acid) or various ionic liquids；It is described organic
Solvent can be carbonates, ethers, sulfone class, phosphate base solvent and nitrile.Wherein carbonates (such as propylene carbonate,
Ethylene carbonate, propene carbonate, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate, diethyl carbonate etc.)；Ethers is (such as
1,3- dioxolanes, glycol dimethyl ether etc.)；Sulfone class (such as ethylmethane sulfonate, sulfolane)；Phosphate base solvent (methyl
Dimethyl phosphonate etc.)；One or more of nitrile (such as acetonitrile, malononitrile, adiponitrile).
Design principle of the present invention is as follows:
Metal sulfide cathode will form after first charge-discharge irreversible product lithium sulfide and metal nanoparticle (due to
Its conversion reactionInvertibity is poor, and part reaction product is difficult to reversible transformation and is
Metal sulfide), and irreversible the product sulfur lithium can be used as active material in 2.4V (vs.Li/Li+) reactThe method (referring to applying for a patent 201310093023.7) injected by electrochemical charge, control gold
Belong to sulfide electrode potential, it can be achieved that regulation electrode electro Chemical reacts and state, so that " activation " irreversible product lithium sulfide, makes
Metal sulfide after regulation reacts energy storage with the reversible transformation of sulphur with lithium sulfide as anode.
It advantages of the present invention and has the beneficial effect that:
1, electrochemical charge injection process method proposed by the present invention can effectively to the electro-chemical activity of metal sulfide into
Row regulation, to obtain the metal sulfide electrode with positive-active.
2, the method for electrochemical regulating and controlling metal sulfide proposed by the present invention has popularity.The present invention is based on metal vulcanizations
Object has the poor reversible substantive characteristics of conversion reaction, can be used for various metal sulfides.
3, the simple process for the realization metal sulfide positive-active that the present invention designs, different batches repeatability is strong, is easy to
Extensive amplification production.
Detailed description of the invention:
Fig. 1 is that the present invention injects the method schematic diagram for realizing metal sulfide positive-active by electrochemical charge.
Fig. 2 is after regulating and controlling by electrochemical charge injection method, to vulcanize the electrochemical reaction schematic diagram of molybdenum electrode.By regulation
It afterwards, can not reversion products Li2S " activation " changes reaction in positive section
Fig. 3 is chemical property of the molybdenum sulfide anode in ethers electrolyte；In figure: it is permanent not regulate and control vulcanization molybdenum electrode (a)
Flow charging and discharging curve；(b) with 2.8V (vs.Li/Li+) it is blanking voltage, regulate and control after cure molybdenum anode constant current charge-discharge curve；
(c) with 3.1V (vs.Li/Li+) it is blanking voltage, regulate and control after cure molybdenum anode constant current charge-discharge curve；(d) with 3.1V
(vs.Li/Li+) it is blanking voltage, regulate and control after cure molybdenum stability of anode energy.
Fig. 4 is the chemical property for vulcanizing molybdenum electrode in lipid electrolyte；(a) regulates and controls the anode constant current of after cure molybdenum in figure
Charging and discharging curve；(b) regulate and control after cure molybdenum anode constant current charge-discharge curve.
Specific embodiment:
The present invention is illustrated below with reference to embodiment.
Realize the electrochemical treatment process of metal sulfide positive-active as shown in Figure 1: by metal sulphur in following embodiment
As working electrode, lithium piece is used as to electrode and reference electrode compound electrode, is assembled into half-cell, to metal sulfide electrode into
The injection of row electrochemical charge.Coordination electrode current potential makes metal sulfide change reaction, and obtaining can not reversion products --- metal
Nano particle and lithium sulfide；Then coordination electrode current potential " activation " lithium sulfide, and stablize electrode cycle by circulation in advance, thus
It obtains stablizing positive (with specific reference to step (2)).
Fig. 2 is the reaction schematic diagram of metal sulfide anode after electric potential regulating.After electric potential regulating, metal sulfide electrode
Stable phase transformation reaction can occur in positive section:
Comparative example 1
Using molybdenum sulfide as working electrode (70wt.% molybdenum sulfide, the mixing of 20wt.% conductive additive 10wt.% binder
Coating stainless steel collector is applied after uniformly), lithium piece is used as to electrode and reference electrode, 1M LiTFSI+DOL/DME+2%LiNO3For
Electrolyte, in positive section (1.7~3.1V (vs.Li/Li+)) carry out constant current charge-discharge test.Shown in 3 (a) as shown in the figure, not
Vulcanization molybdenum electrode through electric potential regulating, without charge and discharge platform (electrochemical reaction does not occur), capacity is lower, illustrates electrode at this
Potential region does not have electro-chemical activity.
Embodiment 1
Using molybdenum sulfide as working electrode, (70wt.% molybdenum sulfide, 20wt.% conductive additive, 10wt.% binder are mixed
Coating stainless steel collector is applied after closing uniformly), lithium piece is used as to electrode and reference electrode, carries out electrochemical charge to vulcanization molybdenum electrode
Injection.Lipid electrolyte (1M LiPF6+EC/DEC) is used first, carries out vulcanization molybdenum electrode to be discharged to 0.01V (vs.Li/Li+), the conversion reaction that molybdenum sulfide occurs at this time is Then extremely by electrode charge
1.4V(vs.Li/Li+), can get can not reversion products molybdenum nano particle and lithium sulfide (due to reactionInvertibity is poor).Electrode is transferred in ethers electrolyte (1M LiTFSI+
DOL/DME+2%LiNO3) charge to 2.8V (vs.Li/Li+), " activation " lithium sulfideIt is then right
Electrode carries out constant current charge-discharge, and (potential region is 1.7V~2.8V (vs.Li/Li+), recycle 20 times) and constant pressure to 1.7V
(vs.Li/Li+), stable anode can be obtained.Shown in 3 (b) as shown in the figure, compared to the vulcanization molybdenum electrode (Fig. 3 not regulated and controled
(a)), the molybdenum sulfide capacity after regulation dramatically increases, and the vulcanization molybdenum electrode after illustrating regulation has positive-active.
Embodiment 2
Using molybdenum sulfide as working electrode, (70wt.% molybdenum sulfide, 20wt.% conductive additive, 10wt.% binder are mixed
Coating stainless steel collector is applied after closing uniformly), lithium piece is used as to electrode and reference electrode, carries out electrochemical charge to vulcanization molybdenum electrode
Injection.Lipid electrolyte (1M LiPF6+EC/DEC) is used first, by molybdenum sulfide electrode discharge to 0.01V (vs.Li/Li+),
At this time molybdenum sulfide occur conversion reaction be Then by electrode charge to 1.4V
(vs.Li/Li+), can get can not reversion products molybdenum nano particle and lithium sulfide (due to reactionInvertibity is poor).Electrode is transferred in ethers electrolyte (1M LiTFSI+
DOL/DME+2%LiNO3) charge to 3.1V (vs.Li/Li+), " activation " lithium sulfideThen to electricity
Pole carries out constant current charge-discharge, and (potential region is 1.7V~3.1V (vs.Li/Li+), recycle 20 times) and constant pressure to 1.7V (vs.Li/
Li+), stable anode can be obtained.Shown in 3 (c) as shown in the figure, compared to the vulcanization molybdenum electrode (Fig. 3 (a)) not regulated and controled, regulation
Molybdenum sulfide capacity afterwards dramatically increases, and the vulcanization molybdenum electrode after illustrating regulation has positive-active；And compared to Fig. 3 (b),
(3.1V (vs.Li/Li in the higher situation of blanking voltage+)), the vulcanization molybdenum electrode after regulation has apparent reaction platform (allusion quotation
The sulphur anode charge and discharge platform of type), illustrate that irreversible lithium sulfide is more efficiently and is converted into sulphur.In addition, the vulcanization after regulation
Molybdenum electrodeization is great good cyclical stability, and coulombic efficiency 99.8% (such as Fig. 3 (d)), anode can be used for after illustrating regulation
Lithium secondary battery ethers electrolyte system
Embodiment 3
Using molybdenum sulfide as working electrode, (70wt.% molybdenum sulfide, 20wt.% conductive additive, the mixing of 10% binder are equal
Coating stainless steel collector is applied after even), lithium piece is used as to electrode and reference electrode, carries out electrochemical charge note to vulcanization molybdenum electrode
Enter.Lipid electrolyte (1M LiPF6+EC/DEC) is used first, by molybdenum sulfide electrode discharge to 0.01V (vs.Li/Li+), this
When molybdenum sulfide change reactionThen by electrode charge to 1.4V (vs.Li/
Li+), can get can not reversion products molybdenum nano particle and lithium sulfide (due to reaction
Invertibity is poor).Electrode is transferred in lipid electrolyte (1M LiPF6+EC/DMC) and charges to 3V (vs.Li/Li+), " swash
It is living " lithium sulfideThen carrying out constant current charge-discharge to electrode, (potential region is 1.6V~3V (vs.Li/
Li+), recycle 20 times) and constant pressure to 1.6V (vs.Li/Li+), stable anode can be obtained.Shown in 4 (a) as shown in the figure, after regulation
Molybdenum sulfide have electro-chemical activity.In addition, the anode after regulation has good cyclical stability, coulombic efficiency 99.9%
(such as Fig. 4 (b)), the anode after illustrating regulation can be used for lithium ion battery lipid electrolyte system.
Claims (5)
1. a kind of metal sulfide is applied to the method for cathode plate for lithium secondary battery, it is characterised in that: this method comprises the following steps:
(1) using metal sulfide as active electrode material, it is prepared into metal sulfide electrode；
(2) by electrochemical charge inject method prepared metal sulfide electrode is regulated and controled, make its 1.7V~
Blanking voltage (vs.Li/Li+) with after electro-chemical activity, that is, obtain the cathode plate for lithium secondary battery；
In step (2), prepared metal sulfide electrode is regulated and controled by the method that electrochemical charge injects specific
Process are as follows: using the metal sulfide electrode of step (1) preparation as working electrode, lithium piece is used as to electrode and reference electrode, together
When electrolyte is added, injected by electrochemical charge, to realize the regulation to the electro-chemical activity of metal sulfide；
Injecting the regulation active process of metal sulfide by electrochemical charge is that electrode electricity is carried out by control blanking voltage
Chemically active adjustment, process are as follows: make electrode in potential region 0.01V~1.4V (vs.Li/Li first+) constant current charge-discharge one
It is secondary, it changes and reacts MxSy+2yLi++2ye-<—>xM+yLi2S utilizes the poorly reversible spy of metal sulfide conversion reaction
Point, acquisition can not reversion products --- transition metal nanoparticles M and lithium sulfide (Li2S)；Then regulation electrode potential reaches cut-off
Voltage (vs.Li/Li+), so that can not the lithium sulfide in reversion products change and react Li2S<—>2Li++S；Finally in anode
Section 1.7V~blanking voltage (vs.Li/Li+) constant current charge-discharge circulation is carried out, stablize electro-chemical activity to obtain and have
Metal sulfide anode, i.e. cathode plate for lithium secondary battery.
2. metal sulfide according to claim 1 is applied to the method for cathode plate for lithium secondary battery, it is characterised in that: step
(1) in, the metal sulfide is that one or more of molybdenum sulfide, cobalt sulfide, iron sulfide, copper sulfide and nickel sulfide are compound.
3. metal sulfide according to claim 1 is applied to the method for cathode plate for lithium secondary battery, it is characterised in that: step
(1) in, the manufacture craft of metal sulfide electrode are as follows: metal sulfide, binder and conductive agent are successively carried out to ingredient, applied
Cloth, tabletting and slice obtain.
4. metal sulfide according to claim 1 is applied to the method for cathode plate for lithium secondary battery, it is characterised in that: step
(2) in, after carrying out electrochemical regulating and controlling processing to prepared metal sulfide electrode, gained cathode plate for lithium secondary battery is in voltage belt
Between 1.7V~blanking voltage (vs.Li/Li+) react in charge and discharge process.
5. metal sulfide according to claim 1 is applied to the method for cathode plate for lithium secondary battery, it is characterised in that: described
Electrolyte is organic electrolyte or ionic liquid, in which: the organic electrolyte is perchlorate, tetrafluoroborate, double trifluoros
Sulfonyl methane imine lithium, hexafluorophosphate or trifluoromethyl sulfonic acid are dissolved in solution formed in organic solvent, described to have
Solvent is one or more of carbonates, ethers, sulfone class, phosphate base solvent and nitrile, and the carbonates are third
In alkene carbonic ether, ethylene carbonate, propene carbonate, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate and diethyl carbonate
One or more；The ethers is 1,3- dioxolanes and/or glycol dimethyl ether；The sulfone class be ethylmethane sulfonate or
Sulfolane；The phosphate base solvent is dimethyl methyl phosphonate；The nitrile is one of acetonitrile, malononitrile and adiponitrile
Or it is several.
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| CN101278426A (en) * | 2005-09-26 | 2008-10-01 | 奥克斯能源有限公司 | Lithium-sulphur battery with high specific energy |
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| CN101278426A (en) * | 2005-09-26 | 2008-10-01 | 奥克斯能源有限公司 | Lithium-sulphur battery with high specific energy |
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