CN106299246A - Metal secondary batteries composite negative pole and application thereof - Google Patents

Metal secondary batteries composite negative pole and application thereof Download PDF

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Publication number
CN106299246A
CN106299246A CN201610835690.1A CN201610835690A CN106299246A CN 106299246 A CN106299246 A CN 106299246A CN 201610835690 A CN201610835690 A CN 201610835690A CN 106299246 A CN106299246 A CN 106299246A
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metal
negative pole
carrier material
lithium
secondary batteries
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CN106299246B (en
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郭玉国
左彤彤
殷雅侠
邓奇
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381Alkaline or alkaline earth metals elements
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381Alkaline or alkaline earth metals elements
    • H01M4/382Lithium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of metal secondary batteries composite negative pole and preparation method, compare the smooth Copper Foil of direct carried metal as metal secondary batteries negative pole, described metal secondary batteries composite negative pole has high power capacity, long-life, the advantages such as stable circulation, simultaneously, the carrier material that this composite negative pole comprises is with low cost, metal secondary batteries composite negative pole preparation process based on this carrier material is simple, the metal secondary batteries using this secondary cell composite negative pole disclosure satisfy that high-energy-density, long-life, the conditions such as safety and stability, and be expected to be applied in high-energy-density device, it is with a wide range of applications.

Description

Metal secondary batteries composite negative pole and application thereof
Technical field:
The invention belongs to field of electrochemical power source, be specifically related to metalloid secondary cell composite negative pole and a preparation method, High power capacity based on this composite negative pole, long-life, the metal secondary batteries of safety and answering at high-energy-density power supply system thereof With.
Background technology:
In recent years, along with the popularization of the energy storage system such as electric automobile, intelligent grid, people are for high-energy density secondary electricity The demand of cell body system is the most urgent.
Metal secondary batteries system is that a class uses the metals such as lithium, sodium, magnesium directly as the secondary cell body of battery cathode System, has the theoretical energy density considerably beyond conventional lithium ion battery, and as a example by lithium-sulfur rechargeable battery, theoretical energy density is high Reach 2654wh/kg, and in coming years even a period of time, be likely to be breached the actual energy density of 500-600wh/kg.Due to The high-energy-density of metal secondary batteries so that it is be expected to become energy storage device of future generation and be applied to intelligent grid, electronic vapour In the energy storage devices such as car.
At present, the subject matter that in metal secondary batteries, metal negative electrode faces is: (1) is non-homogeneous heavy on metal negative electrode surface During the long-pending dendrite caused and following cycle, dendrite pierces through the cell safety problem that barrier film causes battery short circuit to be brought; (2) in cyclic process, constantly exposure metal surface in the electrolytic solution is reacted with electrolyte contacts and is caused battery coulombic efficiency Low problem;Therefore, the application of metal negative electrode must effectively solve above-mentioned two problems.
At present, for the problem that effectively solution dendrite and coulombic efficiency are low, can improve by adding additive at electrolyte Coulombic efficiency (such as Nat Commun, 2015.6:p.7436.), the method can not fundamentally solve metal negative electrode and be circulated throughout In journey repeatedly with electrolyte contacts reacting, be unsuitable for long-life batteries system;Or by between metal negative electrode and barrier film Increase artificial protective layer can effectively dendrite inhibition growth (as patent CN104966814A, CN104617259A, CN105280886A), but the method preparation condition requires higher and process is loaded down with trivial details, is unsuitable for large-scale production and application, separately Outer modification negative pole inevitably increases negative pole weight, thus reduces cathode specific capacity.Therefore, high power capacity, safety, circulation are prepared The metal negative electrode of life-span length is for constructing high-energy, long-life, safe and reliable metal secondary batteries system important in inhibiting.
At present, there are reports to prepare composition metal second electrode by design, and patent CN104716330A is prepared for Three-dimensional porous collector for carried metal negative pole as metal secondary batteries negative pole, but the method preparation process is the most numerous Trivial and suitable content of metal is relatively low;Composite carbon skeleton microsphere diameter prepared by patent CN105374991A be 100 μm with In, aperture is within 50nm, and above-mentioned condition is entirely different with this patent protection content;Patent CN104466095A prepares complex lithium The preparation method that the used heat pressing process of paper tinsel relates to from this patent is different, and two above patent is limited to preparation method and the most only fits For cathode of lithium;Although patent CN101043077A uses similar material to this patent, but above-mentioned patent uses this material Improve the performance of sodium polysulfide/bromine battery with carrying transition metal as conductive substrates.
Summary of the invention:
The invention provides a kind of metal secondary batteries composite negative pole, this metal composite negative pole has specific capacity height, coulomb The advantages such as efficiency is high, voltage polarizing is little, have extended cycle life, it is critical only that after repeatedly cyclic process, this negative pole and through phase Compared with metal negative electrode (such as lithium, sodium, magnesium) prepared by condition, it is possible to be effectively improved the coulombic efficiency during circulating battery, and And produce without obvious dendrite, thus increase the life-span of battery.Meanwhile, the carrier material comprised in this composite negative pole is with low cost, Metal composite negative pole preparation process based on this carrier material is simple, and uses this composite negative pole can avoid using collector, Thus indirectly improve the specific discharge capacity of electrode.Therefore this invention has the potentiality of actual application.
Present invention firstly provides a kind of metal secondary batteries composite negative pole, be made up of carrier material and carried metal, described Metal refers to directly to use one or more in lithium metal, sodium, magnesium, and described carrier material is made up of carbon fiber, fiber A diameter of 10-50 μm, the specific surface area of carrier material is 100-600m2/ g, pore volume is 0.2-8cm3/ g, average pore size is 0.05- 400 μm, carrier material thickness is 0.5-5mm, it is preferable that a diameter of 20-40 μm of described fiber, and described specific surface area is 300- 600m2/ g, pore volume is 6-8cm3/ g, average pore size is 50-100 μm, and carrier material thickness is 0.8-1.2mm.Preferably, described load Body material is without chemical surface treatment, such as, processes without alkaline reagent.
It is further preferred that described carrier material is graphite felt, carbon cloth, carbon fiber form three-dimensional net structure.
The present invention further provides the preparation method of above-mentioned metal secondary batteries composite negative pole, lithium metal, sodium, magnesium are passed through Electrochemical deposition, melted infiltration etc. are either physically or chemically carried in described carrier material, preferably electrochemical deposition method.
It is further preferred that with carrier material as negative electrode, metal (such as lithium, sodium, magnesium) is anode, at 0.1-4mA/cm2's Under electric current density, at deposited on supports 2-20mAh/cm2Metal simple-substance, it is preferable that described electric current density is 0.5-2mAh/ cm2, deposition is 3-10mAh/cm2, it is highly preferred that described electric current density is 0.5-1mAh/cm2, deposition is 6-8mAh/ cm2
It is further preferred that metal (such as lithium, sodium, magnesium) and carrier material are placed in inert atmosphere and are warming up to 180-500 DEG C, to calcine 1-5h, make metal penetrate in carrier material, it is preferable that described calcining heat is 200-450 DEG C, calcination time is 2-3h。
The present invention further provides a kind of metal secondary batteries, the metal composite negative pole using above-mentioned preparation method to prepare is made For battery cathode.
The present invention further provides the metal secondary batteries of the negative pole using above-mentioned negative pole or above-mentioned preparation method to prepare High-energy-density, have extended cycle life, application in the energy storage device of safety and stability.
This carrier material is used for preparing metal secondary batteries negative pole and has the advantage that (1) Large ratio surface can have Effect reduces electric current density, enables metal in its surface uniform load;(2) big pore volume represents material and has higher theory Load capacity;(3) electric conductivity well ensures that material can provide good conductive network;Three above advantage is in theory This material bright is suitable for the preparation of metal secondary batteries negative pole.
A kind of metal secondary batteries using above-mentioned metal secondary batteries composite negative pole to assemble, wherein metal secondary batteries is multiple Close negative pole and can improve coulombic efficiency, increase cycle life and safety, described metal secondary batteries refer to use lithium metal, One or more in sodium, magnesium etc. are as the secondary cell system of negative pole.
Use high-energy-density that this metal composite negative pole material assembled, have extended cycle life, the metal two of safety and stability Primary cell application in energy storage device, belongs to protection scope of the present invention too.
Accompanying drawing illustrates:
Fig. 1 is the electron scanning micrograph of graphite felt.
Fig. 2 is the Raman spectrogram of graphite felt.
Fig. 3 is graphite felt load 8mAh/cm in embodiment 12Electron scanning micrograph after lithium metal.
Fig. 4 is graphite felt load 8mAh/cm in embodiment 12Electron scanning micrograph after lithium metal circulation 5 circle.
Fig. 5 is that embodiment 1 is at 1mA/cm2The constant current charge-discharge curve chart of the 35th circle circulation under current density condition.
Fig. 6 is the electron scanning micrograph of common Copper Foil in comparative example 1.
Fig. 7 is Copper Foil load 8mAh/cm in comparative example 12Electron scanning micrograph after lithium metal.
Fig. 8 is Copper Foil load 8mAh/cm in comparative example 12Electron scanning micrograph after lithium metal circulation 5 circle.
Fig. 9 is embodiment 1 and the circulation-coulombic efficiency comparison diagram in comparative example 1.
Detailed description of the invention:
Below in conjunction with specific embodiment, the invention will be further described.
Experimental technique described in following embodiment, if no special instructions, is conventional method;Described reagent and material Obtain from commercial channels.
Embodiment 1:
(1) process of graphite felt carrier
The graphite felt (purchased from Beijing graphite factory) used in experiment is made up of carbon fiber, and carbon fiber diameter is as seen from Figure 1 10 μm, record this graphite felt materials unit mass specific surface area 454m2/ g, unit mass pore volume is 6.4cm3/ g, average pore size is 100 μm, thickness is about 1mm, and quality is 5.7mg.Fig. 2 is the Raman spectrogram of graphite felt, IG/ID=1.16.
Graphite felt is washed into the electrode slice size of Φ=10mm, made graphite felt electrode dehydrated alcohol is rinsed some Secondary, until totally, dry stand-by.
(2) lithium metal composite negative pole based on graphite felt is prepared
With graphite felt materials as negative electrode, metal lithium sheet is anode, at 1.1mA/cm2Electric current density under, pass through electrochemistry The method of deposition loads 8mAh/cm in graphite felt hole2Lithium metal.
After the electron micrograph of Fig. 3 can be seen that carried metal lithium, lithium metal be distributed in graphite felt hole and Surface, substantial amounts of lithium metal deposition does not cause obvious Li dendrite.
(3) lithium metal secondary battery is assembled with above-mentioned composite negative pole
The lithium anode of above-mentioned preparation and suitable positive pole, electrolyte, barrier film are assembled available lithium metal secondary electricity Pond.
In the present embodiment, for testing the character such as the coulombic efficiency of this negative pole, cyclical stability, still with lithium sheet for electrode, And use above-mentioned electrolyte, barrier film to assemble lithium metal secondary battery.
(4) lithium metal secondary battery electrochemical properties test
Use blue electricity battery test system to above-mentioned lithium metal secondary battery at 1mA/cm2Perseverance is carried out under current density condition Stream charge-discharge test, Fig. 4 is the electron micrograph on graphite felt surface, as seen from the figure stone after circulation after circulating battery 5 encloses The lithium of ink felt electrode surface deposition is more uniform, does not has obvious Li dendrite to occur.Fig. 5 is the constant current charge-discharge of the 35th circle circulation Figure, it may be said that bright still stable at battery after the circulation of 500 hours, and polarization is less.Through calculating, load 8mAh/cm2 After lithium anode there is the reversible specific discharge capacity of 1100mAh/g.
Fig. 9 is the secondary cell composite negative pole secondary battery negative pole cycle efficieny with Copper Foil load lithium of graphite felt load lithium Comparison diagram, there is fluctuation, subsequently results in battery short circuit in the secondary battery negative pole of Copper Foil load lithium cycle efficieny when 15 circle, and stone The secondary battery negative pole of ink felt load lithium remains to keep the coulomb of about 98% to imitate after 47 circles circulation (up to 750 hours) Rate.
Embodiment 2:
Difference from Example 1 is that the thickness of graphite felt carrier is about 3mm, and electrode slice quality is 13.9mg, is used for Electrochemical deposition of metal lithium.After tested, load 8mAh/cm2After lithium anode there is the reversible specific capacity of 450mAh/g.
Embodiment 3:
Difference from Example 1 is lithium metal deposition, and the combination electrode in the present embodiment is by carrying in graphite felt Body deposits 16mAh/cm2Lithium metal, through test, load 16mAh/cm2Lithium anode there is 2200mAh/g can Inverse specific capacity.
Embodiment 4:
Difference from Example 1 is to prepare metallic sodium negative pole based on graphite felt carrier, similarly, with graphite felt material Material is negative electrode, and metallic sodium sheet is anode, by the method for electrochemical deposition at graphite felt supported on carriers 8mAh/cm2Metal Sodium.
Embodiment 5:
Difference from Example 1 is to prepare magnesium metal negative pole based on graphite felt carrier, similarly, with graphite felt material Material is negative electrode, and metal magnesium sheet is anode, by the method for electrochemical deposition at graphite felt supported on carriers 8mAh/cm2Metal Magnesium.
Embodiment 6:
Difference from Example 1 is that lithium metal is carried in graphite felt carrier by the method using melted infiltration.
Lithium metal ingot is put on the graphite felt pole piece substituted the bad for the good, is heated to 450 DEG C in an inert atmosphere, calcining at constant temperature 2h, Test for assembling lithium metal secondary battery after natural cooling.
Embodiment 7:
Difference from Example 6 is under inert atmosphere that melted process of osmosis is heated to 200 DEG C, and calcining at constant temperature 2h is treated Test for lithium metal secondary battery after natural cooling.
Embodiment 8:
Difference from Example 1 is to use carbon cloth as carrier material for depositing lithium metal.Carbon cloth unit mass Specific surface area 454m2/ g, unit mass pore volume is 2.5cm3/g.Similarly, with carbon cloth as negative electrode, metal lithium sheet is anode, passes through The method of electrochemical deposition is by 8mAh/cm2Lithium metal be carried on carbon cloth, and for lithium metal secondary battery test.
Comparative example 1:
Other conditions are the most same as in Example 1, and difference is to load 8mAh/cm2The Copper Foil of lithium metal is as two Primary cell negative pole, the most again using lithium metal as electrode and this secondary battery negative pole are assembled into full battery testing surface topography and The cycle performance of this negative pole.
Fig. 6 is smooth copper foil surface electron scanning micrograph;Fig. 7 is the scanning electron of copper foil surface after deposition Microphotograph, it appeared that copper foil surface has intensive fibrous metal lithium existence from figure;Fig. 8 for modify cathode of lithium with The stereoscan photograph on cathode of lithium surface is modified, by scheming after lithium metal secondary battery circulation 5 circle that electrode assembling is become by lithium metal Visible, covered by substantial amounts of irreversible product through 5 circle circulation rear electrode surfaces, the coulomb having a strong impact on negative pole is imitated by this Rate and cycle life.
Comparative example 2:
Other conditions are the most same as in Example 1, and difference is in graphite felt carrier material to load 25mAh/cm2's Lithium metal, tests lithium metal as electrode and this secondary battery negative pole are assembled into full battery equally afterwards.
Comparative example 3:
Difference from Example 1 is first graphite felt to be carried out 1mol/L potassium hydroxide solution activation processing 5h, with Increase graphite felt materials specific surface area.After recording activation, graphite felt materials unit mass specific surface area is 834m2/ g, unit mass Pore volume is 2.9cm3/g.Similarly, with the graphite felt after activation as negative electrode, metal lithium sheet is anode, by electrochemical deposition Method is by 8mAh/cm2Lithium metal be carried on carbon cloth, and for lithium metal secondary battery test.
The performance test table of table 1 embodiment 1-8 and comparative example 1-2
Wherein, specific capacity quality based on carrier material or Copper Foil calculates, after coulombic efficiency is stable circulation Coulombic efficiency.
In sum, to have high power capacity, long-life, circulation steady for the metal secondary batteries composite negative pole after graphite felt load lithium The advantage such as fixed, high-energy-density, long-life, safety are steady to use the metal secondary batteries of this secondary cell composite negative pole disclosure satisfy that Surely requirement is waited.Meanwhile, this secondary cell composite negative pole is with low cost, and preparation process is simple, and suitable reality is applied and produces.Cause This, the metal secondary batteries that metal composite negative pole based on graphite felt carrier provided by the present invention prepares is expected at high energy Metric density device is applied, is with a wide range of applications.
Finally illustrating, above example is merely to illustrate specific embodiments and the unrestricted present invention, this area Those of ordinary skill, according to the main contents of the present invention and design, can carry out accommodation or the equivalent of simplicity, therefore this Bright protection domain should be as the criterion with the protection domain described by claims.

Claims (9)

1. a metal secondary batteries composite negative pole, is made up of carrier material and carried metal, and described metal refers to directly use One or more in lithium metal, sodium, magnesium, it is characterised in that described carrier material is made up of carbon fiber, fiber a diameter of 10-50 μm, the specific surface area of carrier material is 100-600m2/ g, pore volume is 0.2-8cm3/ g, average pore size is 0.05-400 μm, Carrier material thickness is 0.5-5mm, it is preferable that a diameter of 20-40 μm of described fiber, and described specific surface area is 300-600m2/ G, pore volume is 6-8cm3/ g, average pore size is 50-100 μm, and carrier material thickness is 0.8-1.2mm.
Composite negative pole the most according to claim 1, it is characterised in that described carrier material is graphite felt or carbon cloth, by carbon Fiber forms three-dimensional net structure;Preferably, the Raman spectrogram of described graphite felt, IG/ID=1.16.
3. the preparation method of the metal secondary batteries composite negative pole described in claim 1 or 2, by lithium metal, sodium or magnesium by choosing From electrochemical deposition, being either physically or chemically carried in described carrier material of melted infiltration, preferably electrochemical deposition side Method.
Preparation method the most according to claim 3, it is characterised in that: with carrier material as negative electrode, metal (as lithium, sodium, Magnesium, preferably lithium) it is anode, at 0.1-4mA/cm2Electric current density under, at deposited on supports 2-20mAh/cm2Metal simple-substance, Preferably, described electric current density is 0.5-2mAh/cm2, deposition is 3-10mAh/cm2
Preparation method the most according to claim 3, it is characterised in that: metal such as lithium, sodium, magnesium and carrier material are placed in lazy Property atmosphere in be warming up to 180-500 DEG C, calcine 1-5h, make metal penetrate in carrier material, it is preferable that described calcining heat is 200-450 DEG C, calcination time is 2-3h.
6. a metal secondary batteries, it is characterised in that the metal composite negative pole using the preparation method of claim 3 to prepare is made For battery cathode.
7. the metal two of negative pole prepared by the negative pole of use claim 1 or 2 or the preparation method of any one of claim 3-5 Primary cell high-energy-density, have extended cycle life, application in the energy storage device of safety and stability.
8. the composite negative pole material that one of claim 1-3 is described purposes in avoiding Li dendrite.
Purposes the most according to claim 8, it is characterised in that at 1mA/cm2Constant current charge-discharge is carried out under current density condition Test, does not has the growth of Li dendrite or the most a small amount of Li dendrite after circulation 5 circle.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN108933258A (en) * 2018-06-27 2018-12-04 淄博火炬能源有限责任公司 The preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium
WO2019109398A1 (en) * 2017-12-04 2019-06-13 中国科学院化学研究所 Ultra-thin lithium metal composite body, preparation method therefor and use thereof
CN110752346A (en) * 2018-07-23 2020-02-04 北京好风光储能技术有限公司 Back-to-back deposition type metal cathode and back-to-back deposition type metal cathode battery

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CN104752682A (en) * 2015-03-16 2015-07-01 山东玉皇新能源科技有限公司 Preparation method of sulphur/carbon composite cathode material for lithium sulphur battery
CN105514438A (en) * 2015-12-25 2016-04-20 清华大学深圳研究生院 Sodium-ion battery electrode material, electrode and battery
CN105789559A (en) * 2016-04-21 2016-07-20 清华大学 Flexible lithium metal cell negative pole and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN104752682A (en) * 2015-03-16 2015-07-01 山东玉皇新能源科技有限公司 Preparation method of sulphur/carbon composite cathode material for lithium sulphur battery
CN105514438A (en) * 2015-12-25 2016-04-20 清华大学深圳研究生院 Sodium-ion battery electrode material, electrode and battery
CN105789559A (en) * 2016-04-21 2016-07-20 清华大学 Flexible lithium metal cell negative pole and preparation method thereof

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Publication number Priority date Publication date Assignee Title
WO2019109398A1 (en) * 2017-12-04 2019-06-13 中国科学院化学研究所 Ultra-thin lithium metal composite body, preparation method therefor and use thereof
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CN108933258A (en) * 2018-06-27 2018-12-04 淄博火炬能源有限责任公司 The preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium
CN110752346A (en) * 2018-07-23 2020-02-04 北京好风光储能技术有限公司 Back-to-back deposition type metal cathode and back-to-back deposition type metal cathode battery
CN110752346B (en) * 2018-07-23 2021-02-12 北京好风光储能技术有限公司 Back-to-back deposition type metal cathode and back-to-back deposition type metal cathode battery

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