CN107768600A - A kind of foam copper base lithium ion cell negative electrode material and preparation method thereof - Google Patents

A kind of foam copper base lithium ion cell negative electrode material and preparation method thereof Download PDF

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CN107768600A
CN107768600A CN201710879789.6A CN201710879789A CN107768600A CN 107768600 A CN107768600 A CN 107768600A CN 201710879789 A CN201710879789 A CN 201710879789A CN 107768600 A CN107768600 A CN 107768600A
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foam copper
foam
preparation
lithium ion
negative electrode
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CN107768600B (en
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林晓明
林佳
牛继亮
彭海军
蔡跃鹏
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South China Normal University
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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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/027—Negative 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
    • 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

Abstract

The invention discloses a kind of foam copper base lithium ion cell negative electrode material and preparation method thereof, the preparation method of the cell negative electrode material comprises the following steps：1) pretreatment of foam copper；2) preparation of Cu MOF/ foam coppers；3) calcination processing of Cu MOF/ foam coppers.The foam copper base lithium ion cell negative electrode material of the present invention has three-dimensional porous structure, BET surface area is big, porosity is big, add the contact area between electrolyte and negative material, and introduce conductive substrates foam copper and Cu MOF are advantageous to electric charge fast transfer, the increase of carbon doping provides more available avtive spot for lithium ion storage, and can effectively alleviate the Volumetric expansion in charge and discharge process, reversible specific capacity is high, good cycling stability；The foam copper base lithium ion cell negative electrode material of the present invention can be directly used as the electrode of adhesive-free and conductive agent, simplify technology for preparing electrode.

Description

A kind of foam copper base lithium ion cell negative electrode material and preparation method thereof
Technical field
The present invention relates to a kind of foam copper base lithium ion cell negative electrode material and preparation method thereof.
Background technology
With the increase of deterioration and the energy resource consumption of environmental problem, new material and new energy will be following most commercial promises Industry.Lithium ion battery (LIBs) is considered as the energy storage device for most having application value, has power density height, cycle life The advantages that length, safety and environmental protection, in the field extensive use such as portable type electronic product, electric automobile, Aero-Space.However, The exploitation of lithium ion battery has certain bottleneck with application.Such as：The theoretical capacity of graphite cathode material is low (372mAh/g), Through the requirement that can not meet high-energy-density；The theoretical capacity of metal or transition metal oxide (TMOs) negative material is higher, But Volumetric expansion is big in charge and discharge process, poor circulation.Therefore, a kind of capacity height of exploitation, cyclical stability are needed badly Good new electrode materials, could meet growing energy stores demand.
Foam copper (CF) has tridimensional network, and porosity is high, and specific surface area is big, is widely used in capacitor and lithium two Primary cell.Metal-organic framework (MOFs) is a kind of new supermolecule composite, is matched somebody with somebody by metal ion or metal cluster with organic The material that body is formed, has controllability passage, specific surface area is big, and granular size is adjustable, is added to negative electrode of lithium ion battery The memory capacity of lithium ion can be improved in material, shows more preferable chemical property.However, existing process is all logical mostly Cross adhesive foam copper or/and metal-organic framework are added in lithium ion battery negative material, the lithium ion being prepared Cell negative electrode material sheet resistance is high, and electrical conductivity is low, and performance of lithium ion battery prepared therefrom is bad, it is difficult to practical application.
The content of the invention
It is an object of the invention to provide a kind of foam copper base lithium ion cell negative electrode material and preparation method thereof.
The technical solution used in the present invention is：
A kind of preparation method of foam copper base lithium ion cell negative electrode material, comprises the following steps：
1) pretreatment of foam copper：Acetone and hydrochloric acid immersion treatment foam copper are first used respectively, then it is clear with second alcohol and water respectively Wash foam copper；
2) preparation of Cu-MOF/ foam coppers：Mantoquita and Isosorbide-5-Nitrae-phthalic acid are dissolved in DMF, add step 1) processing The foam copper crossed, 100~120 DEG C are reacted 40~60 hours, centrifugation, and solid product is washed, dried, obtains Cu-MOF/ Foam copper；
3) calcination processing of Cu-MOF/ foam coppers：Cu-MOF/ foam coppers are placed in pipe furnace, with 2~4 DEG C/min liter Warm speed rises to 550~650 DEG C, is calcined 4~6 hours in nitrogen atmosphere, then be down to room with 4~6 DEG C/min rate of temperature fall Temperature, obtain CuO-Cu2O-C/CF, i.e. foam copper base lithium ion cell negative electrode material.
The mol ratio of mantoquita, 1,4- phthalic acids described in step 2) is (3.5~4.0)：1.
The addition ratio of mantoquita, DMF described in step 2) is 1mol：(5500~6500) mL.
The mol ratio of mantoquita, foam copper described in step 2) is 1：(0.6~1.5).
Mantoquita described in step 2) is Cu (NO3)2、Cu(CH3COO)2、CuCl2At least one of.
It is DMF that solid product, which is carried out washing solvent used, in step 2), is washed 3~5 times.
The temperature that solid product is dried in step 2) is 100~120 DEG C, and drying time is 40~50 hours.
The beneficial effects of the invention are as follows：The foam copper base lithium ion cell negative electrode material of the present invention has three-dimensional porous knot Structure, BET surface area is big, porosity is big, adds the contact area between electrolyte and negative material, and introduces conductive substrates bubble Foam copper and Cu-MOF are advantageous to electric charge fast transfer, and the increase of carbon doping provides more can use for lithium ion storage Avtive spot, and can effectively alleviate the Volumetric expansion in charge and discharge process, reversible specific capacity is high, good cycling stability, Preparation technology is simple.
1) present invention first grows Cu-MOF in foam copper surface in situ, then is heat-treated as from sacrifice template, The multicomponent reactive metal oxides CuO-Cu being prepared2O-C/CF can be directly used as the electricity of adhesive-free and conductive agent Pole, simplify technology for preparing electrode；
2) the mixed-metal oxides CuO-Cu in foam copper base lithium ion cell negative electrode material of the invention2O-C and list Metal oxide is compared, and the activation energy of electronics transfer is lower, and electric conductivity is higher, and can provide stronger redox chemistry and move Power, in addition, the cooperative effect between different component can also greatly improve specific capacity.
Brief description of the drawings
Fig. 1 is the SEM figures and CuO-Cu of the Cu-MOF/ foam coppers in embodiment 12O-C/CF SEM schemes, TEM schemes, HRTEM schemes and element mapping graph.
Fig. 2 is the CuO-Cu in embodiment 12O-C/CF XRD, XPS spectrum figure, Cu 2p3/2High magnification XPS spectrum figure and Nitrogen adsorption-desorption curve figure.
Fig. 3 be the cyclic voltammetry curve of lithium ion battery in embodiment 1, charging and discharging curve, cycle performance test chart and High rate performance test chart.
Embodiment
A kind of preparation method of foam copper base lithium ion cell negative electrode material, comprises the following steps：
1) pretreatment of foam copper：Acetone and hydrochloric acid immersion treatment foam copper are first used respectively, then it is clear with second alcohol and water respectively Wash foam copper；
2) preparation of Cu-MOF/ foam coppers：Mantoquita and Isosorbide-5-Nitrae-phthalic acid are dissolved in DMF, add step 1) processing The foam copper crossed, 100~120 DEG C are reacted 40~60 hours, centrifugation, and solid product is washed, dried, obtains Cu-MOF/ Foam copper；
3) calcination processing of Cu-MOF/ foam coppers：Cu-MOF/ foam coppers are placed in pipe furnace, with 2~4 DEG C/min liter Warm speed rises to 550~650 DEG C, is calcined 4~6 hours in nitrogen atmosphere, then be down to room with 4~6 DEG C/min rate of temperature fall Temperature, obtain CuO-Cu2O-C/CF, i.e. foam copper base lithium ion cell negative electrode material.
Preferably, the mantoquita described in step 2), the mol ratio of Isosorbide-5-Nitrae-phthalic acid are (3.5~4.0)：1.
Preferably, the mantoquita described in step 2), DMF addition ratio are 1mol：(5500~6500) mL.
Preferably, the mantoquita described in step 2), the mol ratio of foam copper are 1：(0.6~1.5).
Preferably, the mantoquita described in step 2) is Cu (NO3)2、Cu(CH3COO)2、CuCl2At least one of.
Preferably, it is DMF solid product to be carried out washing solvent used in step 2), is washed 3~5 times.
Preferably, temperature solid product being dried in step 2) is 100~120 DEG C, and drying time is 40~50 Hour.
The present invention is made further explanation and description with reference to specific embodiment.
Embodiment 1：
A kind of preparation method of foam copper base lithium ion cell negative electrode material, comprises the following steps：
1) pretreatment of foam copper：The foam copper for taking specification to be 30mm × 30mm × 0.5mm, first uses acetone and hydrochloric acid respectively Immersion treatment, then foam copper is cut to 15mm × 15mm × 0.5mm, then clean foam copper with second alcohol and water respectively；
2) preparation of Cu-MOF/ foam coppers：By 2.4g Cu (NO3)2·3H2O and 0.44g 1,4- phthalic acids dissolving In 60mL DMF, the treated foam copper of step 1) is added, ultrasonic disperse 45 minutes, 110 DEG C are reacted 48 hours, 4000rpm Centrifugation 5 minutes, washs solid product with DMF and is washed, then 60 DEG C of dryings 24 hours, obtains Cu-MOF/ foam coppers；
3) calcination processing of Cu-MOF/ foam coppers：Cu-MOF/ foam coppers are placed in pipe furnace, with 3 DEG C/min heating speed Rate rises to 600 DEG C, is calcined 5 hours in nitrogen atmosphere, then is down to room temperature with 5 DEG C/min rate of temperature fall, obtains CuO-Cu2O- C/CF, i.e. foam copper base lithium ion cell negative electrode material.
Foam copper base lithium ion cell negative electrode material prepared by embodiment 1 is cut into diameter 12mm disk, steeped The copper-based anode plate for lithium ionic cell of foam, is then assembled into lithium ion battery.
The SEM figures (a~c, different amplification) and CuO-Cu of Cu-MOF/ foam coppers prepared by embodiment 12O-C/CF SEM figures (d~f, different amplification), TEM figures (g), HRTEM figures (h) and element mapping graph (i) it is as shown in Figure 1；
CuO-Cu in embodiment 12O-C/CF XRD (a), XPS spectrum figure (b), Cu 2p3/2High magnification XPS spectrum figure (c) and nitrogen adsorption-desorption curve figure (d) is as shown in Figure 2；
Cyclic voltammetry curve (a of lithium ion battery in embodiment 1；Be scanned with 0.1mV/s sweep speed), fill Discharge curve (b；Constant current charge/electric discharge is carried out under 0.1A/g current density), cycle performance test chart (c) and forthright again Energy test chart (d) is as shown in Figure 3.
Interpretation of result：
1) as shown in Figure 1：A~c shows that foam copper Surface Creation Cu-MOF, Cu-MOF are the smooth rule cube in surface Body, the length of side are about 5 μm；D~f shows that Cu-MOF becomes the CuO-Cu of surfaces versus rough after calcining2O-C particles；G shows Cu-MOF/ foam coppers form many holes in calcination process；D=0.246nm lattice fringe belongs to Cu in h2O's (111) lattice plane, d=0.253nm lattice fringe belong to CuO (002) lattice plane, suggest the formation of hybrid metal oxidation Thing；I shows Cu, O and C element in CuO-Cu2It is uniformly distributed in O-C/CF.
2) as shown in Figure 2：All diffraction maximums can belong to monoclinic crystal CuO (JCPDS No.45-937), stand in a Square Cu2O (JCPDS No.05-0667) and cube Cu (JCPDS No.70-3039), is not observed other impurities, shows institute Obtain CuO, Cu in product2O and Cu three-phase coexistences；B shows that Cu, O and C element coexist in sample；In c 935.1eV, 941.1eV and The Cu that peak at 943.4eV is belonged in CuO2+, and the Cu that 933.8eV and 932.6eV peak is belonged in foam copper+And Cu；d In there is hysteresis curve clearly IV types thermoisopleth, show CuO-Cu2O-C/CF has typical meso-hole structure.
3) as shown in Figure 3：A is shown in first time cathodic scan, because CuO is reduced to Cu2O (equation 1), There is an obvious peak in 1.16V, and the peak at 0.71V is due to Cu2O is decomposed into Cu (equation 2) and solid electrolyte circle The generation of face (SEI) layer, in initial anodic scan, a clear and definite peak is found that at 2.46V, corresponding to Cu continuous oxidations For CuO (equation 3), in continuous circulation, main reduction is changed into 1.28V and 0.84V, shows in first cycle period There is irreversible transition, it is clear that CV curves become stable, and almost overlapping since second period, it means that Li from The insertion and deintercalation of son have a good invertibity, and related electrochemical reaction is as follows：
2CuO+2Li++2e-→Cu2O+Li2O (1)
Cu2O+2Li++2e-→2Cu+Li2O (2)
Cu+Li2O→CuO+2Li++2e-(3)；
B is shown in first time discharge process, and the electrode shows obvious 1.32~1.10V long discharges platform and 1.08 ~0.67V tilt voltage, it corresponds to from CuO to Cu2O multistep reduction process, and further decompose into Cu and Li2O, with CV curves are consistent, and in second circulation, discharge platform rises to 1.35V, and this is probably lithium ion embedded electrode material for the first time Due to new mutually formation after material, caused by irreversible structure transformation and polarization phenomena.The electrode provides the first of 1986mAh/g The charge specific capacity of beginning specific discharge capacity and 1559mAh/g, coulombic efficiency 78.4%.Large Copacity loss is attributable to irreversible Electrochemical reaction, such as the formation of inevitable SEI layers and the decomposition of electrolyte.After initial cycle, its coulombic efficiency is several 100% is kept, illustrates CuO-Cu2O-C/CF electrodes have good cyclical stability.Obviously, gradually increased specific capacity can The process gradually activated is attributed to, this is the common phenomenon of negative electrode.Compared to CuO-Cu2O-C electrodes are in 100 circulation knots Sharp-decay occurs for Shu Hou, reversible specific capacity, the cyclical stability and high rate performance with extreme difference.And CuO-Cu2O-C/CF electricity Pole can retain 1321mAh/g reversible specific capacity (c), show significant cyclical stability at the end of the 500th circulates；d Show the CuO-Cu under different current densities2The high rate performance of O-C/CF electrodes.Respectively in 0.2A/g, 0.5A/g and 1A/g Under current density, specific capacity is respectively 1124mAh/g, 1007mAh/g and 930mAh/g.Importantly, even in up to 5A/ Under g current density, 753mAh/g high specific capacity is remained in that.It is interesting that when current density returns to 0.1A/g, Electrode almost recovers its original specific capacity, and this shows fabulous high rate performance.
Embodiment 2：
A kind of preparation method of foam copper base lithium ion cell negative electrode material, comprises the following steps：
1) pretreatment of foam copper：The foam copper for taking specification to be 30mm × 30mm × 0.5mm, first uses acetone and hydrochloric acid respectively Immersion treatment, then foam copper is cut to 15mm × 15mm × 0.5mm, then clean foam copper with second alcohol and water respectively；
2) preparation of Cu-MOF/ foam coppers：By 2.0g CuCl2It is dissolved in 90mL's with 0.43g 1,4- phthalic acids In DMF, the treated foam copper of step 1) is added, ultrasonic disperse 45 minutes, 100 DEG C are reacted 50 hours, and 4000rpm centrifuges 5 points Clock, wash solid product with DMF and washed, then 60 DEG C of dryings 24 hours, obtain Cu-MOF/ foam coppers；
3) calcination processing of Cu-MOF/ foam coppers：Cu-MOF/ foam coppers are placed in pipe furnace, with 3 DEG C/min heating speed Rate rises to 550 DEG C, is calcined 6 hours in nitrogen atmosphere, then is down to room temperature with 5 DEG C/min rate of temperature fall, obtains CuO-Cu2O- C/CF, i.e. foam copper base lithium ion cell negative electrode material.
Embodiment 3：
A kind of preparation method of foam copper base lithium ion cell negative electrode material, comprises the following steps：
1) pretreatment of foam copper：The foam copper for taking specification to be 30mm × 30mm × 0.5mm, first uses acetone and hydrochloric acid respectively Immersion treatment, then foam copper is cut to 15mm × 15mm × 0.5mm, then clean foam copper with second alcohol and water respectively；
2) preparation of Cu-MOF/ foam coppers：By 2.2g Cu (CH3COO)2It is dissolved in 0.46g 1,4- phthalic acids In 70mL DMF, add the treated foam copper of step 1), ultrasonic disperse 45 minutes, 120 DEG C are reacted 40 hours, 4000rpm from The heart 5 minutes, wash solid product with DMF and washed, then 60 DEG C of dryings 24 hours, obtain Cu-MOF/ foam coppers；3)Cu- The calcination processing of MOF/ foam coppers：Cu-MOF/ foam coppers are placed in pipe furnace, 650 DEG C are risen to 3 DEG C/min heating rate, Calcined 6 hours in nitrogen atmosphere, then room temperature is down to 5 DEG C/min rate of temperature fall, obtain CuO-Cu2O-C/CF, i.e. foam Copper-based lithium ion battery negative material.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (8)

  1. A kind of 1. preparation method of foam copper base lithium ion cell negative electrode material, it is characterised in that：Comprise the following steps：
    1) pretreatment of foam copper：Acetone and hydrochloric acid immersion treatment foam copper are first used respectively, then clean bubble with second alcohol and water respectively Foam copper；
    2) preparation of Cu-MOF/ foam coppers：Mantoquita and Isosorbide-5-Nitrae-phthalic acid are dissolved in DMF, add what step 1) treated Foam copper, 100~120 DEG C are reacted 40~60 hours, centrifugation, and solid product is washed, dried, obtains Cu-MOF/ foams Copper；
    3) calcination processing of Cu-MOF/ foam coppers：Cu-MOF/ foam coppers are placed in pipe furnace, with 2~4 DEG C/min heating speed Rate rises to 550~650 DEG C, is calcined 4~6 hours in nitrogen atmosphere, then is down to room temperature with 4~6 DEG C/min rate of temperature fall, obtains To CuO-Cu2O-C/CF, i.e. foam copper base lithium ion cell negative electrode material.
  2. 2. preparation method according to claim 1, it is characterised in that：Mantoquita, 1,4- phthalic acids described in step 2) Mol ratio is (3.5~4.0)：1.
  3. 3. preparation method according to claim 1, it is characterised in that：The addition ratio of mantoquita, DMF described in step 2) is 1mol：(5500~6500) mL.
  4. 4. preparation method according to claim 1, it is characterised in that：The mol ratio of mantoquita, foam copper described in step 2) For 1：(0.6~1.5).
  5. 5. preparation method according to claim 1, it is characterised in that：Mantoquita described in step 2) is Cu (NO3)2、Cu (CH3COO)2、CuCl2At least one of.
  6. 6. preparation method according to claim 1, it is characterised in that：Solid product wash in step 2) used Solvent is DMF, is washed 3~5 times.
  7. 7. preparation method according to claim 1, it is characterised in that：The temperature that solid product is dried in step 2) For 100~120 DEG C, drying time is 40~50 hours.
  8. 8. foam copper base lithium ion cell negative electrode material prepared by the method in claim 1~7 described in any one.
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CN110649267A (en) * 2019-08-20 2020-01-03 北京泰丰先行新能源科技有限公司 Composite metal lithium cathode, preparation method and metal lithium battery
CN110649267B (en) * 2019-08-20 2021-05-18 北京泰丰先行新能源科技有限公司 Composite metal lithium cathode, preparation method and metal lithium battery
CN110718689A (en) * 2019-09-03 2020-01-21 华南师范大学 Metal-coated foam copper-based self-supporting lithium cobaltate electrode material and preparation method thereof
CN110534718A (en) * 2019-09-04 2019-12-03 福州大学 A kind of preparation method of transition metal oxide nano-slice array@carbon paper electrode
CN111705315A (en) * 2020-06-28 2020-09-25 北京理工大学 Preparation method of modified copper three-dimensional framework and application of modified copper three-dimensional framework in lithium battery
CN111705315B (en) * 2020-06-28 2021-08-06 北京理工大学 Preparation method of modified copper three-dimensional framework and application of modified copper three-dimensional framework in lithium battery
CN113193193A (en) * 2021-05-14 2021-07-30 河南大学 Application of foam metal loaded transition metal matrix MOF material as battery negative electrode material
CN114068907A (en) * 2021-11-16 2022-02-18 江苏科技大学 CuO @ Cu-BTC composite electrode with rod-shaped structure and preparation method thereof

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