CN106803571A - One kind has high-energy, high magnification and long-life carbon positive pole and its application - Google Patents

One kind has high-energy, high magnification and long-life carbon positive pole and its application Download PDF

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CN106803571A
CN106803571A CN201510837533.XA CN201510837533A CN106803571A CN 106803571 A CN106803571 A CN 106803571A CN 201510837533 A CN201510837533 A CN 201510837533A CN 106803571 A CN106803571 A CN 106803571A
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carbon
positive pole
energy
long
life
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CN106803571B (en
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李峰
单旭意
王宇作
王大伟
成会明
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Institute of Metal Research of CAS
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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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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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Abstract

There is high-energy, high magnification and long-life carbon positive pole and its application the invention discloses one kind, belong to electrochemical energy storage technical field.The present invention effectively realizes the protection to carbon electrode material by electrochemistry pre-coated method, so as to obtain high power capacity, high magnification, the carbon positive electrode of long circulation life.The present invention can be effectively used for alkali metal, alkaline-earth metal (lithium, sodium, potassium, magnesium, calcium etc.) ion battery and alkali metal, alkaline-earth metal ions (lithium, sodium, potassium, magnesium, calcium etc.) capacitor is used as positive pole, can obtain and have high-energy concurrently, high power, the energy storage device of the characteristic such as long circulation life.The present invention has technical process simple and compatible with existing process simultaneously, and for improving device performance effect is significant, therefore with great application prospect.

Description

One kind has high-energy, high magnification and long-life carbon positive pole and its application
Technical field
The present invention relates to the technical field of electrochemical energy storage, and in particular to one kind has high-energy, high magnification With long-life carbon positive pole and its application.
Background technology
Effective storage of the clean energy resourcies such as solar energy, wind energy, electric automobile and portable type electronic product it is quick Development all proposes higher and higher requirement to electrochemical energy storing device.And wherein lithium ion battery is still current The main flow device for using.However as the large-scale application of lithium battery, the problem of lithium resource will be increasingly serious.With Sodium, potassium, magnesium, calcium are the alkali metal of representative, alkaline-earth metal ions battery and alkali metal, alkaline-earth metal ions electricity Container will turn into the direction of future development.However, alkali metal, alkaline-earth metal ions identical with lithium ion battery Battery and alkali metal, alkaline-earth metal ions capacitor all suffer from same problem：The low capacity of positive electrode, Low range and difference cyclical stability.The development of positive electrode greatly governs electrochemical energy storing device forward Propulsion.Compared to the positive electrode of embedded type, the diversity of carbon material self structure and abundant functional group are Design of material and it is modified and provides capacity high there is provided advantage, while its conductance high for having and ion expands Characteristic is dissipated, excellent high rate performance can be provided.Thus carbon material is considered as following most promising positive electrode One of.
But it is unstable in high voltage potential interval during used in positive pole because carbon material has greater activity in itself, It is easy to be reacted with electrolyte, the performance degradation in cyclic process can be caused, significantly limit it in alkali gold Further applying in category, alkaline-earth metal ions battery and alkali metal, alkaline-earth metal ions capacitor.Therefore such as Where ensure carbon material positive pole high power capacity, it is powerful under the premise of improve its following between positive pole high voltage region Ring stability is current urgent problem.
The content of the invention
There is high-energy, high magnification and long-life carbon positive pole it is an object of the invention to provide one kind and its answer With, the protection to carbon electrode is realized by electrochemistry pre-coated method, it is capable of achieving it and presses down in electrochemical process Electrolyte decomposition processed, obtains the carbon electrode of high power capacity, high magnification and long circulation life.The electrode can be effective In alkali metal, alkaline-earth metal (lithium, sodium, potassium, magnesium, calcium etc.) ion battery and alkali metal, alkaline-earth metal from Sub (lithium, sodium, potassium, magnesium, calcium etc.) capacitor is used as positive pole, so that obtain have high-energy concurrently, high power, The electrochemical energy storage part of the characteristics such as long circulation life.
To achieve the above object, the technical solution adopted in the present invention is as follows：
One kind has high-energy, high magnification and long-life carbon positive pole, is prepared in accordance with the following steps：
(1) assembling of carbon electrode：Using carbon electrode as working electrode, lithium piece as to electrode and reference electrode, Carbon electrode, lithium piece and barrier film are assembled into sandwich structure, while adding the electrolyte comprising additive, the electrolysis The content of additive is 0.01~10wt.% in liquid；
(2) the electrochemistry pre-coated treatment of carbon electrode：Carbon electrode after to being assembled through step (1) is in positive polar region Between (4.5V~0.8V vs.Li/Li+) constant-current discharge is carried out, by controlling the additive amount in electrolyte and constant current Discharge time carries out the adjustment of electrochemistry pre-coated effect.When the additive level in electrolyte is When 0.01-10wt.% and discharge time are 5min~50h, the additive in electrolyte is at current potential 0.8-4.5V points Solution, and the thin-layered protective film of uniform fold is formed in carbon electrodes, the diaphragm can block electrolyte from carbon materials Material surface obtains the path of electronics and reaction of decomposing, and can realize the protection to carbon electrode；So as to obtain State high power capacity, high magnification and long-life carbon electrode.
In above-mentioned steps (1), the sandwich structure refers to that carbon electrode, barrier film and lithium piece are arranged in order assembling institute The structure of formation；After being processed through step (2) electrochemistry pre-coated, form organic polymer in carbon electrodes and protect Cuticula, thickness is 0.5nm-100nm.
In above-mentioned steps (1), the additive be LiODFB, dioxalic acid lithium borate, propylene carbonate, Tetrachloro-ethylene, propene sulfonic acid methyl esters, carbonic acid first alkynes, Allyl methyl carbonate, allyl methyl sulfonic acid, carbon Vinyl acetate, fluorinated ethylene carbonate, sulfurous acid butylene, butane sultone, the third sultone, benzyl ring sulfuric acid Ester, 4- methyl isophthalic acids, 3,2- bis- oxazoles thiophene -2,2- dioxide and 4- ethyl -1,3,2- Er oxazole thiophene -2,2- titanium dioxides One or more in thing.
The electrolyte can be organic electrolyte or various ionic liquids；The organic electrolyte refers to perchloric acid Salt, tetrafluoroborate, double trifluoromethanesulfonimide lithiums, hexafluorophosphate or trifluoromethyl sulfonic acid etc. are having The solution formed in machine solvent；The organic solvent can be molten for carbonates, ethers, sulfone class, phosphate base One or more in agent and nitrile；Wherein carbonates are propylene carbonate, ethylene carbonate, propylene carbonate One or more in ester, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate and diethyl carbonate；Ethers It is 1,3- dioxolanes or glycol dimethyl ether etc.；Sulfone class is ethylmethane sulfonate or sulfolane etc.；Phosphate base Solvent is dimethyl methyl phosphonate etc.；Nitrile is one or more in acetonitrile, malononitrile and adiponitrile etc..
Active electrode material (carbon material) is activated carbon, template carbon, NACF, carbon in the carbon positive pole Aerosol, CNT, Graphene, cracking charcoal, graphite and carbon containing polymer are (including polypyrrole, poly- It is thiophene, polyaniline, poly- to benzene, polyacene etc.) in the composite of one or more.
In above-mentioned steps (1), carbon positive pole before assembling is made as common process, will active electrode material (carbon Material), binding agent and conductive agent carry out dispensing, coating, compressing tablet and section and obtain.
The present invention preparation with high-energy, high magnification and long-life carbon positive pole be applied to alkali metal, alkali Earth metal (lithium, sodium, potassium, magnesium, calcium etc.) ion battery and alkali metal, alkaline-earth metal ions (lithium, sodium, Potassium, magnesium, calcium etc.) capacitor is used as positive pole, so as to obtain have high-energy, high power and long circulation life etc. concurrently The electrochemical energy storage part of characteristic.Concrete application method is：Will be with high-energy, high magnification and long-life Carbon positive pole, barrier film and negative pole carry out lamination assembling successively, be packaged after electrolyte injection；By it is aging, Degassing and secondary encapsulation are to obtain the energy storage device with characteristics such as high-energy, high power and long circulation lifes.
Design principle of the present invention is as follows：
The carbon electrode prepared using common process, lithium electrode and barrier film are assembled into sandwich structure by the present invention first, And after injecting the electrolyte containing a certain amount of additive, thin layer is formed in carbon electrodes using electrochemistry pre-coated Organic polymer diaphragm, so as to effectively realize the protection to carbon electrode, it is to avoid electrolyte is straight with carbon surface Contact, and being reacted during electrochemistry cycle charge-discharge causes to decompose.So as to obtain high power capacity, height The carbon electrode of multiplying power and long circulation life.The electrode can be effectively used for alkali metal, alkaline-earth metal (lithium, sodium, potassium, Magnesium, calcium etc.) ion battery and alkali metal, alkaline-earth metal ions (lithium, sodium, potassium, magnesium, calcium etc.) capacitor Used as positive pole, acquisition has the energy storage device of the characteristics such as high-energy, high power, long circulation life concurrently.
The present invention is put during electrochemistry pre-coated by controlling additive level in electrolyte and constant current The electric time, allow the additive in positive pole interval (4.5V-0.8V vs.Li/Li+) interior decomposition, and in carbon electricity Pole surface carries out film forming.During this period, additive is partly or completely decomposed generation diaphragm.In addition In the interval that agent is decomposed, discharge time is more long, and film forming thickness is bigger.Constant-current discharge electric current is smaller simultaneously, Quality of forming film is higher, easier that electrode material is adequately protected.
Compared to prior art, the present invention achieves following advantage and beneficial effect：
1st, electrochemistry pre-coated process approach proposed by the present invention can be protected effectively to carbon positive pole, so as to obtain High power capacity, high magnification, the carbon positive pole of long circulation life.
2nd, electrochemistry pre-coated process approach proposed by the present invention has popularity, can be used for above-mentioned various carbon materials And organic electrolyte.
3rd, carbon electrode prepared by the present invention, can be used for alkali metal, alkaline-earth metal ions battery and alkali metal, alkaline earth Metal ion capacitor can be greatly improved related energy storage device, energy density, power as positive electrode Characteristic, particularly cyclical stability, widen its application field.
4th, the carbon positive pole preparation process is simple of high power capacity proposed by the present invention, high magnification, long-life feature is different Batch repeatability is strong, it is easy to extensive to amplify production.
Brief description of the drawings
Fig. 1 is electrochemistry pre-coated process schematic；In figure：Land regions shown in dotted line are oxalic acid difluoro boric acid Lithium is decomposed, the time required to abscissa correspondence electrochemistry pre-coated process.
Fig. 2 is the schematic diagram that electrochemistry pre-coated process processes carbon electrode；In figure：(a) initial carbon positive pole；(b) Electrochemistry pre-coated process processes carbon positive pole；C the carbon positive pole after () circulation, due to its high activity, electrolyte exists Electrode surface is persistently decomposed, and accessory substance is persistently piled up in electrode surface and causes electrode to inactivate.Electrolyte and electricity Interpolar ion transport resistance increases, and electrode high rate performance and cyclical stability are all reduced；Electrification after (d) circulation Pre-coated process treatment carbon positive pole, Surface coating diaphragm, due to the presence of diaphragm, electrode structure is stable, High rate performance and cyclical stability are excellent.
Fig. 3 is the electrification that different LiODFB additive capacity treatment Graphene electrodes are used for lithium ion battery Learn performance；In figure：The electrochemistry pre-coated process of (a) difference LiODFB addition；(b) different grass The electrochemistry pre-coated process treatment Graphene electrodes of sour difluoro lithium borate addition are used for lithium ion cell positive High rate performance；The electrochemistry pre-coated process treatment Graphene electricity of (c, d) difference LiODFB addition Pole is used for the cyclical stability of lithium ion cell positive.
Fig. 4 is the chemical property that electrochemistry pre-coated process treatment Graphene positive pole is used for lithium-ion capacitor； In figure：A () high rate performance is contrasted；B () cycle performance is contrasted.
Fig. 5 is the lithium-ion capacitor and existing report that Graphene positive pole is processed using electrochemistry pre-coated process The performance comparison of high-performance lithium ion capacitor；In figure：(a) energy density-power density diagram；(b) 1000 times Cycle performance is contrasted.
Specific embodiment
The present invention is illustrated with reference to embodiment.Electrochemistry pre-coated process in following examples is as schemed Shown in 1；Using corresponding carbon electrode as working electrode, lithium piece as to electrode and reference electrode, while using The esters electrolyte of a certain amount of LiODFB is added to carry out half-cell assembling；The esters electrolyte is Lithium hexafluoro phosphate is formed in being dissolved in ethylene carbonate and dimethyl carbonate, and the concentration of wherein lithium hexafluoro phosphate is 1mol/L.Then the constant-current discharge for carrying out low current to it is to 1.1V.LiODFB is in 1.7V vs. Li/Li+Decomposition can carbon electrodes formed uniform fold, thin layer organic polymer diaphragm.
Fig. 2 is the schematic diagram that electrochemistry pre-coated process processes carbon electrode, initial carbon positive pole (Fig. 2 (a)) warp After circulation, due to its high activity, electrolyte is persistently decomposed in electrode surface, and accessory substance is held in electrode surface Continuous accumulation causes electrode to inactivate, the increase of ion transport resistance, electrode high rate performance and circulation between electrolyte and electrode Stability is all reduced (Fig. 2 (c))；And initial carbon positive pole (Fig. 2 (a)) is first through electrochemistry pre-coated of the present invention Process treatment, Surface coating diaphragm (Fig. 2 (b)), then be circulated, due to the presence of diaphragm, electrode Stability Analysis of Structures, high rate performance and cyclical stability are excellent (Fig. 2 (d)).
Embodiment 1
Using Graphene electrodes as working electrode (80% Graphene, 10% binding agent, 10% conductive additive Stainless (steel) wire collector is coated after well mixed), lithium piece as to electrode and reference electrode, while using 0.5wt% LiODFB as additive esters electrolyte (1M lithium hexafluoro phosphates/ethylene carbonate+carbonic acid two Methyl esters) Graphene electrodes are carried out with the treatment of electrochemistry pre-coated process as electrolyte.The Graphene that will be obtained is just Pole is named as A-G-0.5.Specific schematic diagram is as shown in Figure 1：The constant current that Graphene electrodes carry out low current is put Electricity is to 1.1V.LiODFB is in 1.7V vs.Li/Li+Decomposition can be formed uniformly on Graphene electrodes surface Covering, the diaphragm of thin layer.The corresponding constant current of electrochemistry pre-coated process processing procedure is shown in Fig. 3 (a) Discharge curve.1.7V vs.Li/Li+Land regions correspond to electrochemistry pre-coated process the zone of action.Fig. 3 (b) It is performance of lithium ion battery test.Relative to Graphene electrodes (G), the A-G-0.5 of pre-coated is used for lithium-ion electric Pond positive pole shows more excellent high rate performance and specific capacity higher.Simultaneously relative to Graphene electrodes (G), 400 cyclical stabilities of A-G-0.5 have obtained certain raising, and 54.7% is brought up to from 48.8%.
Embodiment 2
Using Graphene electrodes as working electrode (80% Graphene, 10% binding agent, 10% conductive additive Stainless (steel) wire collector is coated after well mixed), lithium piece as to electrode and reference electrode, while using 1wt% LiODFB as additive esters electrolyte (1M lithium hexafluoro phosphates/ethylene carbonate+carbonic acid two Methyl esters) Graphene electrodes are carried out with the treatment of electrochemistry pre-coated process as electrolyte.The Graphene that will be obtained is just Pole is named as A-G-1.Specific schematic diagram is as shown in Figure 1：Graphene electrodes are carried out with the constant-current discharge of low current To 1.1V.LiODFB is in 1.7V vs.Li/Li+Decomposition can be formed on Graphene electrodes surface and uniformly covered Lid, the diaphragm of thin layer.Show that the corresponding constant current of electrochemistry pre-coated process processing procedure is put in Fig. 3 (a) Electric curve.1.7V vs.Li/Li+Land regions correspond to electrochemistry pre-coated process the zone of action.Fig. 3 (b) It is performance of lithium ion battery test.Relative to Graphene electrodes (G), the A-G-1 of pre-coated is used for lithium ion battery Positive pole shows more excellent high rate performance and specific capacity higher.Simultaneously relative to Graphene electrodes (G), 400 cyclical stabilities of A-G-1 have obtained certain raising, and 73.7% is brought up to from 48.8%.
Embodiment 3
Using Graphene electrodes as working electrode (80% Graphene, 10% binding agent, 10% conductive additive Stainless (steel) wire collector is coated after well mixed), lithium piece as to electrode and reference electrode, while using 2wt% LiODFB as additive esters electrolyte (1M lithium hexafluoro phosphates/ethylene carbonate+carbonic acid two Methyl esters) Graphene electrodes are carried out with the treatment of electrochemistry pre-coated process as electrolyte.The Graphene that will be obtained is just Pole is named as A-G-2.Specific schematic diagram is as shown in Figure 1：Graphene electrodes are carried out with the constant-current discharge of low current To 1.1V.LiODFB is in 1.7V vs.Li/Li+Decomposition can be formed on Graphene electrodes surface and uniformly covered Lid, the diaphragm of thin layer.Show that the corresponding constant current of electrochemistry pre-coated process processing procedure is put in Fig. 3 (a) Electric curve.1.7V vs.Li/Li+Land regions correspond to electrochemistry pre-coated process the zone of action.Fig. 3 (b) It is performance of lithium ion battery test.Relative to Graphene electrodes (G), the A-G-2 of pre-coated is used for lithium ion battery Positive pole shows more excellent high rate performance and specific capacity higher.Simultaneously relative to Graphene electrodes (G), 400 cyclical stabilities of A-G-2 have obtained certain raising, and 98.3% is brought up to from 48.8%.
Embodiment 4
Using Graphene electrodes as working electrode (80% Graphene, 10% binding agent, 10% conductive additive Stainless (steel) wire collector is coated after well mixed), lithium piece as to electrode and reference electrode, while using 5wt% LiODFB as additive esters electrolyte (1M lithium hexafluoro phosphates/ethylene carbonate+carbonic acid two Methyl esters) Graphene electrodes are carried out with the treatment of electrochemistry pre-coated process as electrolyte.The Graphene that will be obtained is just Pole is named as A-G-5.Specific schematic diagram is as shown in Figure 1：Graphene electrodes are carried out with the constant-current discharge of low current To 1.1V.LiODFB is in 1.7V vs.Li/Li+Decomposition can be formed on Graphene electrodes surface and uniformly covered Lid, the diaphragm of thin layer.Show that the corresponding constant current of electrochemistry pre-coated process processing procedure is put in Fig. 3 (a) Electric curve.1.7V vs.Li/Li+Land regions correspond to electrochemistry pre-coated process the zone of action.Fig. 3 (b) It is performance of lithium ion battery test.Relative to Graphene electrodes (G), the A-G-5 of pre-coated is used for lithium ion battery Positive pole shows more excellent high rate performance and specific capacity higher.Simultaneously relative to Graphene electrodes (G), 400 cyclical stabilities of A-G-5 have obtained certain raising, and 76.6% is brought up to from 48.8%.
Embodiment 5
Electrochemistry pre-coated process processes Graphene electrodes (A-G-2) and causes device for lithium-ion capacitor positive pole Part shows excellent high-energy-density (160Wh/kg) and high power density (20kW/kg).It is significantly higher than Using the lithium-ion capacitor of Graphene positive pole (G).It is also simultaneously one of top performance of current report, has Great application prospect.If Fig. 4 (a) is two kinds of high rate performance contrasts of lithium-ion capacitor；Fig. 4 (b) is two kinds 1000 cyclical stability contrasts of lithium-ion capacitor.
And, the lithium-ion capacitor using electrochemistry pre-coated process treatment Graphene positive pole (A-G-2) represents Go out splendid cyclical stability, be only 0.011% per loop attenuation amount.Equally be current report high-performance lithium from Stability highest in sub-capacitor.As shown in Figure 5.

Claims (9)

  1. It is 1. a kind of that there is high-energy, high magnification and long-life carbon positive pole, it is characterised in that：The high power capacity, The preparation process of high magnification and long-life carbon electrode comprises the following steps：
    (1) assembling of carbon electrode：Using carbon electrode as working electrode, lithium piece as to electrode and reference electrode, Carbon electrode, lithium piece and barrier film are assembled into sandwich structure, while adding the electrolyte comprising additive, the electrolysis The content of additive is 0.01~10wt.% in liquid；
    (2) the electrochemistry pre-coated treatment of carbon electrode：Carbon electrode after to being assembled through step (1) is in positive polar region Between 4.5V-0.8V (vs.Li/Li+) constant-current discharge is carried out, after discharge time 5min~50h, that is, obtain the height Capacity, high magnification and long-life carbon electrode.
  2. 2. according to claim 1 with high-energy, high magnification and long-life carbon positive pole, its feature exists In：In step (1), the sandwich structure refer to carbon electrode, barrier film and lithium piece be arranged in order assembling formed Structure.
  3. 3. according to claim 1 with high-energy, high magnification and long-life carbon positive pole, its feature exists In：In the electrolyte comprising additive, the additive be LiODFB, dioxalic acid lithium borate, Propylene carbonate, tetrachloro-ethylene, propene sulfonic acid methyl esters, carbonic acid first alkynes, Allyl methyl carbonate, pi-allyl first Base sulfonic acid, ethylene carbonate, fluorinated ethylene carbonate, sulfurous acid butylene, butane sultone, the third sultone, Phenyl Cyclic Sulfate, 4- methyl isophthalic acids, the oxazole thiophene -2,2- dioxide of 3,2- bis- and the oxazole thiophene of 4- ethyls -1,3,2- two One or more in -2,2- dioxide.
  4. 4. according to claim 1 or 3 with high-energy, high magnification and long-life carbon positive pole, it is special Levy and be：In the electrolyte comprising additive, electrolyte is organic electrolyte or various ionic liquids；Institute It refers to perchlorate, tetrafluoroborate, double trifluoromethanesulfonimide lithiums, hexafluorophosphate to state organic electrolyte Or the solution that trifluoromethyl sulfonic acid dissolving is formed in organic solvent, the organic solvent is carbonates, ether One or more in class, sulfone class, phosphate base solvent and nitrile, wherein：Carbonates be propylene carbonate, Ethylene carbonate, propene carbonate, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate and diethyl carbonate In one or more, ethers be DOX or glycol dimethyl ether, sulfone class be ethylmethane sulfonate or Sulfolane, phosphate base solvent is dimethyl methyl phosphonate, and nitrile is in acetonitrile, malononitrile and adiponitrile Plant or several.
  5. 5. according to claim 1 with high-energy, high magnification and long-life carbon positive pole, its feature exists In：In the carbon positive pole active electrode material (carbon material) be activated carbon, templated porous charcoal, NACF, It is carbon aerosol, CNT, Graphene, cracking charcoal, graphite, polypyrrole, polythiophene, polyaniline, poly- right The composite of one or more in benzene and polyacene.
  6. 6. there is high-energy, high magnification and long-life carbon positive pole according to claim 1 or 5, it is special Levy and be：In step (1), the manufacture craft of the carbon positive pole before assembling is：By active electrode material (carbon material), Binding agent and conductive agent carry out dispensing, coating, compressing tablet and section and obtain.
  7. 7. according to claim 1 with high-energy, high magnification and long-life carbon positive pole, its feature exists In：In step (2), during constant-current discharge, the additive in electrolyte is in the current potential 0.8-4.5V time-divisions Solution, and the thin-layered protective film of uniform fold is formed in carbon electrodes, realize the protection to carbon electrode；In carbon electricity The thin-layered protective film that pole surface is formed is organic polymer, and thickness is 0.5nm-100nm.
  8. 8. a kind of application with high-energy, high magnification and long-life carbon positive pole as claimed in claim 1, It is characterized in that：Should have high-energy, high magnification and long-life carbon positive pole be applied to alkali metal-ion battery, Alkaline-earth metal ions battery, alkali metal ion capacitor or alkaline-earth metal ions capacitor as positive pole, so as to obtain The electrochemical energy storage part of high-energy, high power and long circulation life must be had concurrently.
  9. 9. the application with high-energy, high magnification and long-life carbon positive pole according to claim 8, its It is characterised by：There is the application process of high-energy, high magnification and long-life carbon positive pole to be for this：Will be with high energy Amount, high magnification and long-life carbon positive pole, barrier film and negative pole carry out lamination assembling successively, after electrolyte injection It is packaged；It is to obtain that there is high-energy, high power and long circulation life by aging, degassing and secondary encapsulation Energy storage device.
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CN108511720A (en) * 2018-04-04 2018-09-07 深圳市然然电子有限公司 A kind of lithium battery
CN112271334A (en) * 2020-10-26 2021-01-26 哈尔滨工业大学 Cathode film-forming additive for magnesium metal battery with metal magnesium as cathode material and application thereof
CN114094166A (en) * 2021-11-19 2022-02-25 北京胜能能源科技有限公司 Lithium ion battery non-aqueous electrolyte and lithium ion battery

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CN103680972A (en) * 2012-09-10 2014-03-26 中国科学院金属研究所 High-energy high-power density lithium ion supercapacitor and assembling method thereof
CN104058395A (en) * 2014-07-11 2014-09-24 武汉理工大学 Method for preparing graphene by carrying out ultrasonic treatment on lithium intercalated graphite
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CN103680972A (en) * 2012-09-10 2014-03-26 中国科学院金属研究所 High-energy high-power density lithium ion supercapacitor and assembling method thereof
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CN108511720A (en) * 2018-04-04 2018-09-07 深圳市然然电子有限公司 A kind of lithium battery
CN112271334A (en) * 2020-10-26 2021-01-26 哈尔滨工业大学 Cathode film-forming additive for magnesium metal battery with metal magnesium as cathode material and application thereof
CN112271334B (en) * 2020-10-26 2022-01-25 哈尔滨工业大学 Cathode film-forming additive for magnesium metal battery with metal magnesium as cathode material and application thereof
CN114094166A (en) * 2021-11-19 2022-02-25 北京胜能能源科技有限公司 Lithium ion battery non-aqueous electrolyte and lithium ion battery
CN114094166B (en) * 2021-11-19 2023-12-12 北京胜能能源科技有限公司 Non-aqueous electrolyte of lithium ion battery and lithium ion battery

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