CN107768600B - 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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CN107768600B
CN107768600B CN201710879789.6A CN201710879789A CN107768600B CN 107768600 B CN107768600 B CN 107768600B CN 201710879789 A CN201710879789 A CN 201710879789A CN 107768600 B CN107768600 B CN 107768600B
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foam copper
preparation
negative electrode
lithium ion
mof
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CN107768600A (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 materials and preparation method thereof, and the preparation method of the cell negative electrode material is the following steps are included: the 1) pretreatment of foam copper；2) preparation of Cu-MOF/ foam copper；3) calcination processing of Cu-MOF/ foam copper.Foam copper base lithium ion cell negative electrode material of the invention has three-dimensional porous structure, BET surface area is big, porosity is big, increase the contact area between electrolyte and negative electrode material, and introduce conductive substrates foam copper and Cu-MOF is conducive to charge fast transfer, the increase of carbon doping provides more available active site for lithium ion storage, and the Volumetric expansion in charge and discharge process can be effectively relieved, reversible specific capacity is high, good cycling stability；Foam copper base lithium ion cell negative electrode material of the 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 materials and preparation method thereof.
Background technique
With the deterioration of environmental problem and the increase of energy consumption, new material and new energy will be the 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, is widely applied in fields such as portable electronic product, electric car, aerospaces.However, The exploitation and application of lithium ion battery have certain bottleneck.Such as: the theoretical capacity of graphite cathode material is low (372mAh/g), It is not able to satisfy the requirement of high-energy density；Metal or the theoretical capacity of transition metal oxide (TMOs) negative electrode material are higher, But Volumetric expansion is big in charge and discharge process, poor circulation.Therefore, need to develop that a kind of capacity is high, cyclical stability Good new electrode materials, are just able to satisfy growing energy stores demand.
Foam copper (CF) has tridimensional network, and porosity is high, and large specific surface area is widely used in capacitor and lithium two Primary cell.Metal-organic framework (MOFs) is a kind of novel supermolecule composite material, is matched by metal ion or metal cluster with organic The material that body is formed has controllability channel, and large specific surface area, granular size is adjustable, is added to negative electrode of lithium ion battery The memory capacity that lithium ion can be improved in material shows better chemical property.However, prior art is all logical mostly It crosses 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 conductivity is low, and performance of lithium ion battery prepared therefrom is bad, is difficult practical application.
Summary of the invention
The purpose of the present invention is to provide a kind of foam copper base lithium ion cell negative electrode materials 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, comprising the following steps:
1) pretreatment of foam copper: first using acetone and hydrochloric acid immersion treatment foam copper respectively, then clear with second alcohol and water respectively Wash foam copper；
2) preparation of Cu-MOF/ foam copper: mantoquita and Isosorbide-5-Nitrae-phthalic acid are dissolved in DMF, and step 1) processing is added The foam copper crossed, 100~120 DEG C are reacted 40~60 hours, and centrifugation is washed solid product, dried, obtains Cu-MOF/ Foam copper；
3) calcination processing of Cu-MOF/ foam copper: Cu-MOF/ foam copper is placed in pipe furnace, with the liter of 2~4 DEG C/min Warm rate rises to 550~650 DEG C, calcines 4~6 hours in nitrogen atmosphere, then be down to room with the rate of temperature fall of 4~6 DEG C/min Temperature obtains CuO-Cu2O-C/CF, i.e. foam copper base lithium ion cell negative electrode material.
Mantoquita described in step 2), 1,4- phthalic acid molar ratio be (3.5~4.0): 1.
Mantoquita described in step 2), DMF additive amount ratio be 1mol:(5500~6500) mL.
Mantoquita described in step 2), foam copper molar ratio be 1:(0.6~1.5).
Mantoquita described in step 2) is Cu (NO3)2、Cu(CH3COO)2、CuCl2At least one of.
Solid product is carried out washing solvent used being DMF in step 2), is washed 3~5 times.
It is 100~120 DEG C to the temperature that solid product is dried in step 2), drying time is 40~50 hours.
The beneficial effects of the present invention are: foam copper base lithium ion cell negative electrode material of the invention has three-dimensional porous knot Structure, BET surface area is big, porosity is big, increases the contact area between electrolyte and negative electrode material, and introduces conductive substrates bubble Foam copper and Cu-MOF are conducive to charge fast transfer, and the increase of carbon doping provides more available for lithium ion storage Active site, and the Volumetric expansion that can be effectively relieved in charge and discharge process, reversible specific capacity is high, good cycling stability, Preparation process 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 simplifies 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 it is dynamic to provide stronger redox chemistry Power, in addition, the synergistic effect between different component can also greatly improve specific capacity.
Detailed description of the invention
Fig. 1 is the SEM figure and CuO-Cu of the Cu-MOF/ foam copper in embodiment 12The SEM of O-C/CF schemes, TEM schemes, HRTEM figure and element mapping graph.
Fig. 2 is the CuO-Cu in embodiment 12The XRD diagram of O-C/CF, 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.
Specific embodiment
A kind of preparation method of foam copper base lithium ion cell negative electrode material, comprising the following steps:
1) pretreatment of foam copper: first using acetone and hydrochloric acid immersion treatment foam copper respectively, then clear with second alcohol and water respectively Wash foam copper；
2) preparation of Cu-MOF/ foam copper: mantoquita and Isosorbide-5-Nitrae-phthalic acid are dissolved in DMF, and step 1) processing is added The foam copper crossed, 100~120 DEG C are reacted 40~60 hours, and centrifugation is washed solid product, dried, obtains Cu-MOF/ Foam copper；
3) calcination processing of Cu-MOF/ foam copper: Cu-MOF/ foam copper is placed in pipe furnace, with the liter of 2~4 DEG C/min Warm rate rises to 550~650 DEG C, calcines 4~6 hours in nitrogen atmosphere, then be down to room with the rate of temperature fall of 4~6 DEG C/min Temperature obtains CuO-Cu2O-C/CF, i.e. foam copper base lithium ion cell negative electrode material.
Preferably, mantoquita described in step 2), Isosorbide-5-Nitrae-phthalic acid molar ratio are (3.5~4.0): 1.
Preferably, the additive amount ratio of mantoquita, DMF described in step 2) is 1mol:(5500~6500) mL.
Preferably, the molar ratio of mantoquita, foam copper described in step 2) is 1:(0.6~1.5).
Preferably, mantoquita described in step 2) is Cu (NO3)2、Cu(CH3COO)2、CuCl2At least one of.
Preferably, solid product is carried out washing solvent used being DMF in step 2), is washed 3~5 times.
It preferably, is 100~120 DEG C to the temperature that solid product is dried in step 2), drying time is 40~50 Hour.
The present invention will be further explained combined with specific embodiments below and explanation.
Embodiment 1:
A kind of preparation method of foam copper base lithium ion cell negative electrode material, comprising the following steps:
1) pretreatment of foam copper: taking specification is 30mm × 30mm × 0.5mm foam copper, 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 copper: by the Cu (NO of 2.4g3)2·3H2The 1,4- phthalic acid of O and 0.44g dissolves In the DMF of 60mL, the processed foam copper of step 1) is added, ultrasonic disperse 45 minutes, 110 DEG C were reacted 48 hours, 4000rpm Centrifugation 5 minutes, wash solid product with DMF and washed, then 60 DEG C drying 24 hours, obtain Cu-MOF/ foam copper；
3) calcination processing of Cu-MOF/ foam copper: Cu-MOF/ foam copper is placed in pipe furnace, with the heating speed of 3 DEG C/min Rate rises to 600 DEG C, calcines 5 hours, then be down to room temperature with the rate of temperature fall of 5 DEG C/min in nitrogen atmosphere, 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 the disk of diameter 12mm, is steeped The copper-based anode plate for lithium ionic cell of foam, is then assembled into lithium ion battery.
The SEM figure (a~c, different amplification) and CuO-Cu of Cu-MOF/ foam copper prepared by embodiment 12O-C/CF SEM figure (d~f, different amplification), TEM figure (g), HRTEM figure (h) and element mapping graph (i) it is as shown in Figure 1；
CuO-Cu in embodiment 12The XRD diagram (a) of O-C/CF, 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 the sweep speed of 0.1mV/s), fill Discharge curve (b；Constant current charge/electric discharge is carried out under the current density of 0.1A/g), 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, side length are about 5 μm；D~f shows that Cu-MOF becomes the CuO-Cu of surfaces versus rough after calcining2O-C particle；G shows Cu-MOF/ foam copper forms many holes in calcination process；The lattice fringe of d=0.246nm belongs to Cu in h2O's (111) lattice plane, the lattice fringe of d=0.253nm belong to (002) lattice plane of CuO, suggest the formation of mixed metal oxidation Object；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 coexistence；B shows that Cu, O and C element coexist in sample；In c 935.1eV, 941.1eV and Peak at 943.4eV belongs to the Cu in CuO2+, and the peak of 933.8eV and 932.6eV belongs to the Cu in foam copper+And Cu；d In there is hysteresis loop clearly IV type 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, since CuO is reduced to Cu2O (equation 1), There is an apparent 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 has found a specific peak in initial anodic scan at 2.46V, corresponds to Cu continuous oxidation For CuO (equation 3), in continuous circulation, main reduction is changed into 1.28V and 0.84V, shows in first cycle period Occur irreversible transition, it is clear that CV curve becomes stable, and is almost overlapped since second period, it means that Li from The insertion and deintercalation of son have 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, which shows apparent 1.32~1.10V long discharge platform and 1.08 The tilt voltage of~0.67V corresponds to from CuO to Cu2The multistep reduction process of O, and further decompose into Cu and Li2O, with CV curve is consistent, and in second circulation, discharge platform rises to 1.35V, this may be lithium ion insertion 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 capacity loss is attributable to irreversible Electrochemical reaction, such as the decomposition of inevitable SEI layers of formation and electrolyte.After initial cycle, coulombic efficiency is several 100% is kept, illustrates CuO-Cu2O-C/CF electrode has good cyclical stability.Obviously, the specific capacity gradually increased can Due to the process gradually activated, this is the common phenomenon of negative electrode.Compared to CuO-Cu2O-C electrode is tied in 100 circulations Sharp-decay occurs for Shu Hou, reversible specific capacity, has very poor cyclical stability and high rate performance.And CuO-Cu2O-C/CF electricity Pole can retain the reversible specific capacity (c) of 1321mAh/g, show significant cyclical stability at the end of the 500th circulation；d Show the CuO-Cu under different current densities2The high rate performance of O-C/CF electrode.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 if in up to 5A/ Under the current density of g, the high specific capacity of 753mAh/g is still maintained.It is interesting that when current density is restored to 0.1A/g, Electrode almost restores its original specific capacity, this shows fabulous high rate performance.
Embodiment 2:
A kind of preparation method of foam copper base lithium ion cell negative electrode material, comprising the following steps:
1) pretreatment of foam copper: taking specification is 30mm × 30mm × 0.5mm foam copper, 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 copper: by the CuCl of 2.0g2It is dissolved in 90mL's with the 1,4- phthalic acid of 0.43g In DMF, the processed foam copper of step 1) is added, ultrasonic disperse 45 minutes, 100 DEG C were reacted 50 hours, and 4000rpm is centrifuged 5 points Clock washs solid product with DMF and is washed, then 60 DEG C drying 24 hours, obtain Cu-MOF/ foam copper；
3) calcination processing of Cu-MOF/ foam copper: Cu-MOF/ foam copper is placed in pipe furnace, with the heating speed of 3 DEG C/min Rate rises to 550 DEG C, calcines 6 hours, then be down to room temperature with the rate of temperature fall of 5 DEG C/min in nitrogen atmosphere, 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, comprising the following steps:
1) pretreatment of foam copper: taking specification is 30mm × 30mm × 0.5mm foam copper, 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 copper: by the Cu (CH of 2.2g3COO)2It is dissolved in the 1,4- phthalic acid of 0.46g In the DMF of 70mL, be added the processed foam copper of step 1), ultrasonic disperse 45 minutes, 120 DEG C react 40 hours, 4000rpm from The heart 5 minutes, wash solid product with DMF and washed, then 60 DEG C drying 24 hours, obtain Cu-MOF/ foam copper；3)Cu- The calcination processing of MOF/ foam copper: Cu-MOF/ foam copper is placed in pipe furnace, rises to 650 DEG C with the heating rate of 3 DEG C/min, It is calcined 6 hours in nitrogen atmosphere, then room temperature is down to the rate of temperature fall of 5 DEG C/min, obtain CuO-Cu2O-C/CF, i.e. foam Copper-based lithium ion battery negative material.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (8)

1. a kind of preparation method of foam copper base lithium ion cell negative electrode material, it is characterised in that: the following steps are included:
1) pretreatment of foam copper: acetone and hydrochloric acid immersion treatment foam copper are first used respectively, then cleans bubble with second alcohol and water respectively Foam copper；
2) preparation of Cu-MOF/ foam copper: mantoquita and Isosorbide-5-Nitrae-phthalic acid are dissolved in DMF, and it is processed that step 1) is added Foam copper, 100~120 DEG C are reacted 40~60 hours, and centrifugation is washed solid product, dried, obtains Cu-MOF/ foam Copper；
3) calcination processing of Cu-MOF/ foam copper: Cu-MOF/ foam copper is placed in pipe furnace, with the heating speed of 2~4 DEG C/min Rate rises to 550~650 DEG C, calcines 4~6 hours, then be down to room temperature with the rate of temperature fall of 4~6 DEG C/min, obtains in nitrogen atmosphere To CuO-Cu2O-C/ foam copper, i.e. foam copper base lithium ion cell negative electrode material.
2. preparation method according to claim 1, it is characterised in that: mantoquita described in step 2), Isosorbide-5-Nitrae-phthalic acid Molar ratio is (3.5~4.0): 1.
3. preparation method according to claim 1, it is characterised in that: mantoquita described in step 2), DMF additive amount ratio be 1mol:(5500~6500) mL.
4. preparation method according to claim 1, it is characterised in that: the molar ratio of mantoquita described in step 2), foam copper For 1:(0.6~1.5).
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. preparation method according to claim 1, it is characterised in that: wash to solid product in step 2) used Solvent is DMF, is washed 3~5 times.
7. preparation method according to claim 1, it is characterised in that: the temperature that solid product is dried in step 2) It is 100~120 DEG C, drying time is 40~50 hours.
8. the foam copper base lithium ion cell negative electrode material of the preparation of method described in any one of claim 1~7.
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CN110718689B (en) * 2019-09-03 2021-05-18 华南师范大学 Metal-coated foam copper-based self-supporting lithium cobaltate electrode material and preparation method thereof
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