CN105609761B - A kind of application of CuCl/Cu composite materials - Google Patents

A kind of application of CuCl/Cu composite materials Download PDF

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Publication number
CN105609761B
CN105609761B CN201510570652.3A CN201510570652A CN105609761B CN 105609761 B CN105609761 B CN 105609761B CN 201510570652 A CN201510570652 A CN 201510570652A CN 105609761 B CN105609761 B CN 105609761B
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cucl
composite materials
electrode
current collector
copper
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CN105609761A (en
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侯宏英
刘松
刘显茜
段继祥
孟瑞晋
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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 present invention discloses a kind of application of CuCl/Cu composite materials, belongs to exploitation and the research field of new energy materials；The present invention mainly by a step anode oxidation method one layer of cubic phase not soluble in water of metallic copper collection liquid surface in-situ deposition stannous chloride active material, be then assembled into the glove box full of high-purity argon gas with lithium paper tinsel button simulation lithium ion battery.The present invention is bound tightly together homologous material copper current collector and stannous chloride are ingenious by the method for growth in situ, and not only specific surface area is big for the electrode material, but also is tightly combined with copper current collector, contribute to reduction contact resistance.Compared with traditional coating type technique, the technological operation is simple, environmental-friendly, it is easy to amplify, what is more important, helps to alleviate obscission of the active material during long-term charge/discharge, and improves the multiplying power discharging property and charge/discharge cycle performance of lithium ion battery.

Description

A kind of application of CuCl/Cu composite materials
Technical field
The present invention relates to a kind of application of CuCl/Cu composite materials, and in particular to a kind of CuCl/Cu composite materials lithium from Application in sub- battery, belongs to exploitation and the research field of new energy materials.
Background technology
Lithium ion battery is a kind of high efficiency, the green energy-storing device of high-energy-density, has been widely used in removable Dynamic electronic equipment.Electrode material is one of critical component of lithium ion battery, of close concern to each other with the performance of lithium ion battery, is to grind Study carefully one of hot spot.
The technology for preparing electrode of conventional lithium ion battery is physics application process, i.e., by active material and conductive agent（Acetylene It is black）, binding agent（PVDF）Electrode slurry is uniformly mixed into certain proportion, and is applied directly to collection liquid surface and forms.It is based on Electrode prepared by traditional electrode technique is during circulation charge/discharge for a long time, often because being tied between active material and collector Close defective tightness and powder of detached and the circulation charge/discharge service life for reducing electrode, it is therefore necessary to develop novel electrode and prepare work Skill.
Stannous chloride, as a kind of important organic catalyst compound, in petro chemical industry, metallurgical industry, medicineization Learn and had a wide range of applications in numerous industries such as industry, but be also not employed as the correlation text of lithium ion battery electrode material so far Offer report.
The content of the invention
It is an object of the invention to provide the application of CuCl/Cu composite materials, specifically, CuCl/Cu composite materials are used Make the working electrode of lithium ion battery, wherein being that this area prepares lithium-ion electric to electrode, reference electrode, membrane, electrolyte Conventional selection during pond.
Preferably, CuCl/Cu composite materials of the present invention may not need and add additionally when preparing lithium ion battery Conductive agent and binding agent.
Preferably, the present invention is not soluble in water in one layer of metallic copper collection liquid surface growth in situ using a step anodizing The advanced composite material (ACM) CuCl/Cu with cubic phase, specifically include following steps：Using metal copper current collector as work electricity Pole, using platinized platinum as to electrode, to contain Cl-Salting liquid be electrolyte, in 60~600 s of copper current collector surface anodization, Novel composite electrode material is obtained after rinsing well and being dried in vacuo.
Preferably, copper current collector of the present invention is copper foil current collector, foam copper current collector or copper nano-wire collector.
Preferably, it is of the present invention to contain Cl-Salting liquid be sodium chloride solution, Klorvess Liquid or copper chloride solution, salt Cl in solution-Concentration be 0.01~0.1 mol/L.
Preferably, vacuum drying temperature of the present invention is 25~50 DEG C.
Preferably, pH=5~7 of the salting liquid of the present invention containing Cl-.
By scanning electron microscope（SEM）, X-ray energy dispersive spectrometer（EDX）And X-ray diffractometer（XRD） The microstructure of prepared CuCl/Cu electrode materials is characterized, as shown in Figure 1, Figure 2, Figure 3 shows；These results are clearly It is Cubic stannous chloride/carbon/carbon-copper composite material really to indicate obtained sample.
Advantages of the present invention and effect：
The present invention using a step anodizing in metallic copper collection liquid surface growth in situ one layer it is new not soluble in water The stannous chloride with cubic phase（CuCl）Electrode active material, obtains CuCl/Cu combination electrode materials.This compound electric Extremely excellent chemical property can be attributed to the following aspects：（1）It is this compound compared with electrode of the tradition containing binding agent The preparation method of electrode can make active material expose more avtive spots participation electrode reactions, improve the electric discharge ratio of electrode Capacity；（2）Using in-situ method prepare composite material can make active material and collector strong bonded to greatest extent, with up to The electrode material purpose not easily to fall off into long-term cyclic process, is conducive to improve the cyclical stability of electrode.The combination electrode First discharge specific capacity be 103.1 mAh/g, and as the progressively activation of electrode, the specific discharge capacity of electrode further increase Greatly, when being recycled to 50 times, the specific discharge capacity of electrode increases to 215.6 mAh/g, is demonstrated by good charge and discharge cycles and stablizes Property.
Brief description of the drawings
Fig. 1 is respectively to amplify（a）30000 times and the combination electrode material CuCl/Cu of 60,000 times of (b) of SEM schemes
The EDX that Fig. 2 is prepared combination electrode material CuCl/Cu is composed；
The XRD that Fig. 3 is prepared combination electrode material CuCl/Cu is composed；
Fig. 4 is the charge/discharge curve of the combination electrode material CuCl/Cu prepared by embodiment 2；
Fig. 5 is the circulation charge/discharge stability of the combination electrode material CuCl/Cu prepared by embodiment 2；
Fig. 6 is the charge/discharge curve of the combination electrode material CuCl/Cu prepared by embodiment 6.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is simultaneously It is not limited to the content.
Embodiment 1
Using 0.1 mol/L sodium-chloride water solutions of pH=5 as electrolyte solution, using copper foil as working electrode, using platinized platinum as pair Electrode, constant current（5 mA/cm2）60 s of anodic oxidation, rinses well and after 25 DEG C of dryings of vacuum, obtains CuCl/Cu composite materials.
Directly using prepared CuCl/Cu composite materials as working electrode, using lithium paper tinsel as to electrode and reference electrode, with Celgard2500 films are membrane, with containing 1 M LiPF6Ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate （DMC）Mixed liquor be electrolyte, wherein, the volume ratio of EC, DEC and DMC is 1:1:1, then in the hand full of high-purity argon gas Be assembled into button simulation lithium ion battery in casing with lithium paper tinsel, and with the method for constant current charge/discharge test its charge/discharge performance and Cyclical stability.
Embodiment 2
Using 0.1 mol/L sodium-chloride water solutions of pH=5 as electrolyte solution, using copper foil as working electrode, using platinized platinum as pair Electrode, constant current（5 mA/cm2）120 s of anodic oxidation, rinses well and obtains CuCl/Cu composite materials after 25 DEG C of dryings of vacuum.
Do not add extra conductive agent and binding agent, directly using CuCl/Cu composite materials as working electrode, using lithium paper tinsel as pair Electrode and reference electrode, using Celgard2400 films as membrane, with containing 1 M LiPF6Ethylene carbonate (EC) and carbonic acid diethyl The mixed liquor of ester (DEC) is electrolyte, wherein, the volume ratio of EC and DEC are 1:1, then in the glove box full of high-purity argon gas It is interior that button simulation lithium ion battery is assembled into lithium paper tinsel, and it is electrical in the method for constant current charge/discharge to test its discharge charge（Fig. 4）Energy And cyclical stability（Fig. 5）, as seen from the figure, the first discharge specific capacity of the combination electrode is 103.1 mAh/g, and with The progressively activation of electrode, electrode discharge specific capacity slowly increase, and when being recycled to 50 times, specific discharge capacity increases to 215.6 mAh/ g。
Embodiment 3
Using 0.06 mol/L potassium chloride solutions of pH=7 as electrolyte solution, copper foil that wherein working electrode is, to electricity Extremely platinum plate electrode, constant current（5 mA/cm2）240 s of anodic oxidation, rinses well and obtains CuCl/Cu after 40 DEG C of dryings of vacuum Composite material.
Do not add extra conductive agent and binding agent, directly using CuCl/Cu composite materials as working electrode, using lithium paper tinsel as pair Electrode and reference electrode, using Celgard2325 films as membrane, with containing 1 M LiPF6Ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate（DMC）Mixed liquor be electrolyte, wherein the volume ratio of EC, DEC and DMC be 1:1:1, full of height Button simulation lithium ion battery is assembled in the glove box of pure argon, and its charge/discharge performance is tested in the method for constant current charge/discharge And cyclical stability.
Embodiment 4
Using 0.05 mol/L sodium-chloride water solutions of pH=5 as electrolyte, using copper foil as working electrode, platinized platinum be to electrode, Constant current（2.5 mA/cm2）360 s of anodic oxidation, rinses well and obtains CuCl/Cu composite materials after 50 DEG C of dryings of vacuum.
Extra conductive agent and binding agent are not added, directly using CuCl/Cu composite materials as working electrode, with Celgard2400 films are membrane, with containing 1 M LiPF6Ethylene carbonate (EC) and the mixed liquor of diethyl carbonate (DEC) be Electrolyte, wherein, the volume ratio of EC and DEC are 1:1, then button is assembled into lithium paper tinsel in the glove box full of high-purity argon gas Lithium ion battery is simulated, and its charge/discharge performance and cyclical stability are tested in the method for constant current charge/discharge.
Embodiment 5
Using 0.01 mol/L copper chloride solutions of pH=7 as electrolyte, using foam copper as working electrode, platinized platinum is pair Electrode, constant current（0.5 mA/cm2）600 s of anodic oxidation, rinses well and obtains CuCl/Cu composite woods after 45 DEG C of dryings of vacuum Material.
Do not add extra conductive agent and binding agent, directly using CuCl/Cu composite materials as working electrode, using lithium paper tinsel as pair Electrode and reference electrode, using Celgard2500 films as membrane, with LiPF containing 1M6Ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate（DMC）Mixed liquor be electrolyte, wherein the volume ratio of EC, DEC, DMC be 1:1:1, then filling Button simulation lithium ion battery is assembled into the glove box of full high-purity argon gas with lithium paper tinsel, and is tested in the method for constant current charge/discharge Its charge/discharge performance and cyclical stability.
Embodiment 6
Using 0.08 mol/L sodium-chloride water solutions of pH=5 as electrolyte, using copper foil as working electrode, platinized platinum be to electrode, Constant current（0.5 mA/cm2）100 s of anodic oxidation, rinses well and obtains CuCl/Cu composite materials after 30 DEG C of dryings of vacuum.
Do not add extra conductive agent and binding agent, directly using CuCl/Cu composite materials as working electrode, using lithium paper tinsel as pair Electrode and reference electrode, using Celgard2400 films as membrane, with containing 1 M LiPF6Ethylene carbonate (EC) and carbonic acid diethyl The mixed liquor of ester (DEC) is electrolyte, wherein, the volume ratio of EC and DEC are 1:1, then in the glove box full of high-purity argon gas It is interior to be assembled into button simulation lithium ion battery with lithium paper tinsel, and test its charge/discharge performance in the method for constant current charge/discharge（Fig. 6） And cyclical stability, as seen from the figure, battery still suffers from the process of activation, and battery discharge specific capacity is increased by 63.4 initial mAh/g Grow to 161.2 mAh/g during 50 electric discharges.

Claims (3)

  1. A kind of 1. application of CuCl/Cu composite materials, it is characterised in that：CuCl/Cu composite materials are used as the work of lithium ion battery Make electrode, extra conductive agent and binding agent need not be added during lithium ion battery by preparing；
    Preparing for the CuCl/Cu composite materials is as follows：Using metal copper current collector as working electrode, using platinized platinum as to electrode, with Contain Cl-Salting liquid be electrolyte, in 60~600 s of copper current collector surface anodization, after rinsing well and being dried in vacuo Obtain CuCl/Cu composite materials；
    The copper current collector is copper foil current collector, foam copper current collector or copper nano-wire collector；
    It is described to contain Cl-Salting liquid be sodium chloride solution, Klorvess Liquid or copper chloride solution, Cl in salting liquid-Concentration be 0.01~0.1 mol/L.
  2. 2. the application of CuCl/Cu composite materials according to claim 1, it is characterised in that：The vacuum drying temperature is 25~50 DEG C.
  3. 3. the application of CuCl/Cu composite materials according to claim 2, it is characterised in that：The salting liquid containing Cl- PH=5~7.
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CN107686123B (en) * 2017-08-02 2019-12-13 盐城师范学院 solid-liquid interface rapid preparation method of cuprous bromide crystal film material
CN109317170B (en) * 2018-10-15 2021-06-08 盐城师范学院 Preparation method of CuCl/Cu nanorod material with core-shell structure
CN109713311B (en) * 2018-12-20 2021-08-17 南方科技大学 Current collector and preparation method thereof, battery electrode piece and preparation method thereof, and lithium battery
CN109860514B (en) * 2019-03-25 2021-09-07 河北师范大学 Method for changing surface appearance of copper foil of current collector of lithium battery
CN110195234B (en) * 2019-06-11 2021-04-16 中国工程物理研究院材料研究所 Electrooxidation preparation method of copper-cuprous oxide-copper oxide core-shell structure oxygen evolution electrode
CN113555560A (en) * 2020-04-23 2021-10-26 河北零点新能源科技有限公司 Method for improving commercial graphite capacity and rate capability and lithium ion battery
CN112838216A (en) * 2020-11-16 2021-05-25 河北零点新能源科技有限公司 Method for changing color of copper foil of current collector of lithium ion battery

Citations (6)

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Publication number Priority date Publication date Assignee Title
US3661648A (en) * 1969-07-31 1972-05-09 Accumulateurs Fixes Preparation of cuprous chloride electrodes
US4844993A (en) * 1988-08-29 1989-07-04 Altus Corporation Additive to improve voltage regulation in a lithium-copper chloride rechargeable cell
CN101563797A (en) * 2006-12-19 2009-10-21 通用电气公司 Copper-based energy storage device and method
CN101572302A (en) * 2009-03-07 2009-11-04 垦利三合新材料科技有限责任公司 Method for preparing cathode materials of power lithium ion secondary batteries
CN102244304A (en) * 2006-12-19 2011-11-16 通用电气公司 Copper-based energy storage device and method
CN102263258A (en) * 2010-08-10 2011-11-30 中信国安盟固利动力科技有限公司 Positive electrode material of high voltage lithium battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3661648A (en) * 1969-07-31 1972-05-09 Accumulateurs Fixes Preparation of cuprous chloride electrodes
US4844993A (en) * 1988-08-29 1989-07-04 Altus Corporation Additive to improve voltage regulation in a lithium-copper chloride rechargeable cell
CN101563797A (en) * 2006-12-19 2009-10-21 通用电气公司 Copper-based energy storage device and method
CN102244304A (en) * 2006-12-19 2011-11-16 通用电气公司 Copper-based energy storage device and method
CN101572302A (en) * 2009-03-07 2009-11-04 垦利三合新材料科技有限责任公司 Method for preparing cathode materials of power lithium ion secondary batteries
CN102263258A (en) * 2010-08-10 2011-11-30 中信国安盟固利动力科技有限公司 Positive electrode material of high voltage lithium battery

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