CN103531817A - Three-dimensional copper nanowire array current collector for lithium ion battery and production method of three-dimensional copper nanowire array current collector - Google Patents

Three-dimensional copper nanowire array current collector for lithium ion battery and production method of three-dimensional copper nanowire array current collector Download PDF

Info

Publication number
CN103531817A
CN103531817A CN201310488208.8A CN201310488208A CN103531817A CN 103531817 A CN103531817 A CN 103531817A CN 201310488208 A CN201310488208 A CN 201310488208A CN 103531817 A CN103531817 A CN 103531817A
Authority
CN
China
Prior art keywords
copper
lithium ion
ion battery
nanowire array
collector
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201310488208.8A
Other languages
Chinese (zh)
Inventor
陈欣
王瑛
赵成龙
宋春华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jade Emperor flourishing age chemical inc, Shandong
Original Assignee
SHANDONG YUHUANG CHEMICAL CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHANDONG YUHUANG CHEMICAL CO Ltd filed Critical SHANDONG YUHUANG CHEMICAL CO Ltd
Priority to CN201310488208.8A priority Critical patent/CN103531817A/en
Publication of CN103531817A publication Critical patent/CN103531817A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/661Metal or alloys, e.g. alloy coatings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/04Processes of manufacture in general
    • H01M4/0438Processes of manufacture in general by electrochemical processing
    • H01M4/044Activating, forming or electrochemical attack of the supporting material
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/04Processes of manufacture in general
    • H01M4/0471Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/64Carriers or collectors
    • H01M4/70Carriers or collectors characterised by shape or form
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 relates to a three-dimensional copper nanowire array current collector for a lithium ion battery and a production method of the three-dimensional copper nanowire array current collector. The three-dimensional copper nanowire array current collector consists of a copper nanowire array growing on a copper surface. Red copper is employed as a cathode, a solution of sodium hydroxide or potassium hydroxide is employed as electrolyte, stainless steel is employed as an anode, and a saturated mercury chloride electrode is employed as a reference electrode. The production method comprises the following steps of (1) introducing inert gas into an electrolytic bath to remove oxygen, controlling the current density, and electro-oxidizing the cathode to form a Cu(OH)2 thin film on the surface of the red copper to obtain a Cu(OH)2 nanowire array; (2) placing the Cu(OH)2 nanowire array in a hydrogen atmosphere, thermally reducing the Cu(OH)2 nanowire array in a reactor, and naturally cooling to room temperature to obtain the three-dimensional copper nanowire array current collector. A product has high electrical conductivity and an ultra-large specific surface area, and can be produced at a low reaction temperature by simple procedures without a template; a three-dimensional Cu nanowire array has a controllable morphological structure and high uniformity.

Description

Three-dimensional Arrays of Copper Nanowires collector and preparation method thereof for a kind of lithium ion battery
(1) technical field
The present invention relates to three-dimensional Arrays of Copper Nanowires collector and preparation method thereof for a kind of lithium ion battery.
(2) background technology
In recent years, lithium ion battery is at mobile electronic device, electric automobile, standby energy storage, apply gradually in the fields such as intelligent grid, still, is still difficult to meet electric tool, electric automobile (EVs), the power density of hybrid electric vehicle (PHEVs) to battery, the requirement of energy density.The design of tradition lithium ion cell electrode is that negative electrode, active material of positive electrode are mixed in proportion with conductive agent (carbon), binding agent etc., is sprayed on respectively on aluminium foil, Copper Foil collector.The result of this design is: active material is not directly connected with collector, and electron transport ability is poor, the loss that easily comes off, and capacity performance is restricted.Therefore, except finding new electrode material, innovative design collector, to improve the power density of negative electrode, active material of positive electrode, energy density, is also a kind of effective way of improving performance of lithium ion battery.The design of nano-array collector substrate is that the arrays (aluminium, copper, nickel, silicon etc.) such as the good nano wire of conductivity, nanometer rods, nanotube are directly bonded on aluminium foil, Copper Foil to the collector as load negative electrode, active material of positive electrode.This nano-array collector has good conductivity, and the specific area of superelevation is conducive to increase the contact area of electrode/electrolyte, shortens the evolving path of lithium ion, alleviates change in volume and the effect of stress of electrode material while discharging and recharging.At present, existingly prepare micro-/ nano array collector (Nat. Mater. 2006,5,567; Electrochem. Commun. 2008,10, and 1467; Adv. Mater. 2010,22,4978), still, there is Copper Foil collector and active material bad adhesion in report, easily comes off, and causes the poor problem of electrochemistry cycle performance, exists preparation procedure complicated simultaneously, needs template, is difficult to the problems such as commercialization.
(3) summary of the invention
The present invention is in order to make up the defect of prior art, provide a kind of caking property good, be not easy to come off, the three-dimensional Arrays of Copper Nanowires collector for lithium ion battery of electrochemistry cycle performance excellence, its preparation method is provided simultaneously.
The present invention is achieved through the following technical solutions:
With a three-dimensional Arrays of Copper Nanowires collector, it is characterized in that: it is comprised of the Arrays of Copper Nanowires that is grown directly upon copper surface.
A method for three-dimensional Arrays of Copper Nanowires collector for above-mentioned lithium ion battery, is characterized in that, step is as follows:
1) take red copper as anode, NaOH (NaOH) solution or potassium hydroxide (KOH) solution are electrolyte, and stainless steel is negative electrode, and saturated calogreen electrode is reference electrode, first in electrolysis tank, pass into inert gas and remove oxygen (O within the scope of 5~60 ℃ 2), then controlling current density is 0.5~5 mA/cm 2, anodic oxidation 4~30 min, generate blue Cu (OH) at red copper surface 2film, cleans and dries with distilled water, obtains Cu (OH) 2nano-wire array;
2) by Cu (OH) 2nano-wire array is placed in nitrogen atmosphere, in the reactor of 160~200 ℃, and thermal reduction 10~20h, then naturally cool to room temperature, can obtain three-dimensional copper nano-wire battle array collector for lithium ion battery.
The hydrochloric acid of first red copper being put into 0.1~2mol/L soaks 3~5min, then with distilled water, cleans, then cleans with ethanol, dry rear standby.
The concentration of described NaOH (NaOH) solution or potassium hydroxide (KOH) solution is 0.1~4mol/L.
Described inert gas is high-purity N 2or Ar 2.
Described hydrogen is produced by hydrogen generator.
Preparation Cu (OH) 2during the preparation of nano-wire array, the electrode reaction that anode and cathode occurs is as follows:
Anode: (1)
Negative electrode: (2)
Overall reaction: (3)
Cu (OH) 2the chemical reaction that is reduced into Cu is as follows:
(4)
(5)
The invention has the beneficial effects as follows:
It is low by the reaction temperature of three-dimensional Arrays of Copper Nanowires collector that the present invention prepares lithium ion battery, and without template, program is simple, and the appearance structure of three-dimensional Arrays of Copper Nanowires is controlled, has good homogeneity, has industrial rosy prospect.Lithium ion battery prepared by the present invention has good conductivity with three-dimensional Arrays of Copper Nanowires collector, the specific area of superelevation, be conducive to increase the contact area of electrode/electrolyte, shorten the evolving path of lithium ion, alleviate change in volume and the effect of stress of electrode material while discharging and recharging, load lithium ion battery active material of positive electrode, shows good chemical property.
(4) Figure of description
Fig. 1 is the surperficial low range surface sweeping Electronic Speculum figure (SEM) of three-dimensional Arrays of Copper Nanowires collector for lithium ion battery in embodiment mono-;
Fig. 2 is the surperficial high power multiplying power surface sweeping Electronic Speculum figure (SEM) of three-dimensional Arrays of Copper Nanowires collector for lithium ion battery in embodiment mono-;
Fig. 3 is that in embodiment mono-, lithium ion battery is distinguished the X-ray diffractogram (XRD) of carried metal Sn film with three-dimensional Arrays of Copper Nanowires collector (a) and bright copper belt substrate (b);
Fig. 4 is the low range surface sweeping Electronic Speculum figure (SEM) of three-dimensional Arrays of Copper Nanowires collector carried metal Sn film for lithium ion battery in embodiment mono-;
Fig. 5 is the high magnification surface sweeping Electronic Speculum figure (SEM) of three-dimensional Arrays of Copper Nanowires collector carried metal Sn film for lithium ion battery in embodiment mono-;
Fig. 6 is the low range surface sweeping Electronic Speculum figure (SEM) of the copper belt base load metal Sn film of light in embodiment mono-;
Fig. 7 is the high magnification surface sweeping Electronic Speculum figure (SEM) of the copper belt base load metal Sn film of light in embodiment mono-;
Fig. 8 is that in embodiment mono-, lithium ion battery is distinguished the discharge cycles performance map (1C=994mA/g, voltage window is 2.0-0.02 V) of carried metal Sn film with three-dimensional Arrays of Copper Nanowires collector (a) and bright copper belt substrate (b);
Fig. 9 is the surperficial surface sweeping Electronic Speculum figure (SEM) of three-dimensional Arrays of Copper Nanowires collector for lithium ion battery in embodiment bis-;
Figure 10 is the surperficial surface sweeping Electronic Speculum figure (SEM) of three-dimensional Arrays of Copper Nanowires collector for lithium ion battery in embodiment tri-;
Figure 11 is the surperficial low range surface sweeping Electronic Speculum figure (SEM) of three-dimensional Arrays of Copper Nanowires collector for lithium ion battery in embodiment tetra-;
(5) embodiment
Embodiment mono-:
1, the copper belt of 1.5 * 1.5 cm is first removed to the oxide on copper surface for 3 minutes with the hydrochloric acid solution immersion of 0.1M, then with distilled water, clean 5 times, then clean 3 times with ethanol, dry rear standby; Configuration concentration is KOH solution or the NaOH solution for standby of 2M.
2, take copper belt as anode, 304 stainless steel substrates are negative electrode, and saturated calogreen electrode is reference electrode, the about 3cm of anode and cathode spacing, and the KOH solution of 2M or NaOH solution are electrolyte, at 25 ℃, first in electrolysis tank, pass into inert gas (high-purity N 2or Ar 2deng) approximately 30 min are except O 2, then control constant current density 2.5 mA/cm 2, anodic oxidation times 12 min, at the Cu of copper belt Surface Creation blueness (OH) 2film, cleans 3 times dry for standby with distilled water.
3, by the blue Cu (OH) of Surface Creation 2the copper belt of film is put into reactor---and tubular sealed stove, passes into the H being produced by hydrogen generator 2, 3 ℃/min of heating rate, at 180 ℃ of thermal reduction 20h, then naturally cools to room temperature, and the blue film in copper belt surface is transformed into wine-colored Cu nano-wire array.Gained sample carries out surface sweeping Electronic Speculum (SEM) and characterizes, and as depicted in figs. 1 and 2, the nano-wire array of homogeneous is grown in the substrate of copper belt copper, obtains three-dimensional Arrays of Copper Nanowires collector for lithium ion battery.
4, Electrochemical Characterization test:
Above-mentioned lithium ion battery is used for to load lithium ion battery anode material with three-dimensional Arrays of Copper Nanowires collector, at collection liquid surface electro-deposition layer of metal tin (Sn) film (seeing XRD Fig. 3-a, SEM Figure 4 and 5).Electrodeposition condition: plating solution is 0.05M SnSO 4with 1.5M H 2sO 4mixed solution, the saturated calogreen electrode of constant potential-1.0V(is reference electrode), sedimentation time 30 S.
In contrast, at the bright direct electro-deposition one deck Sn film (seeing XRD Fig. 3-b, SEM Fig. 6 and 7) in copper belt surface.Electrodeposition condition: plating solution is 0.05M SnSO 4with 1.5M H 2sO 4mixed solution, the saturated calogreen electrode of constant potential-1.0V(is reference electrode), sedimentation time 120 S.
Have the copper belt of Sn film to be cut into the sequin that diameter is about 14 mm electro-deposition, directly, as the positive pole of lithium ion battery, metal lithium sheet is as negative pole, and electrolyte is by LiPF 6, ethylene carbonate and diethyl carbonate form (LiPF in electrolyte 6concentration is 1M, and the volume ratio of ethylene carbonate and diethyl carbonate is 1:1), barrier film is Celgard2400 microporous polypropylene membrane, is assembled into 2025 type button cells in being full of the glove box of argon gas.
2025 type button cells are carried out to charge-discharge test, Fig. 8-a is the discharge cycles curve chart (1C=994mA/g of three-dimensional Arrays of Copper Nanowires collector base Sn film for lithium ion battery, voltage window is 2.0-0.02 V), discharge capacity is 1337.2 mAh/g first, the capacity after 30 times that circulates is 441.2mAh/g, and capability retention is 40.4%; Fig. 8-b is the discharge cycles curve chart of bright red copper tape base Sn film, and discharge capacity is 1290.7mAh/g first, and the capacity after 30 times that circulates is 211.9 mAh/g, and capability retention is 21.3%.Obviously, lithium ion battery has better charge-discharge performance with three-dimensional Arrays of Copper Nanowires collector for load lithium ion battery negative material Sn film.
Embodiment bis-:
1, the copper belt of 1.5 * 1.5 cm is first removed to the oxide on copper surface for 5 minutes with the hydrochloric acid solution immersion of 1M, then with distilled water, clean 5 times, then clean 3 times with ethanol, dry rear standby; Configuration concentration is KOH solution or the NaOH solution for standby of 1M.
2, take copper belt as anode, 304 stainless steel substrates are negative electrode, and saturated calogreen electrode is reference electrode, the about 3cm of anode and cathode spacing, and the KOH solution of 1M or NaOH solution are electrolyte, at 30 ℃, first in electrolysis tank, pass into inert gas (high-purity N 2or Ar 2deng) approximately 30 min are except O 2, then control constant current density 2.5 mA/cm 2, anodic oxidation time 20min, at the Cu of copper belt Surface Creation blueness (OH) 2film, cleans 3 times dry for standby with distilled water.
3, by the blue Cu (OH) of Surface Creation 2the copper belt of film is put into reactor---and tubular sealed stove, passes into the H being produced by hydrogen generator 2, 3 ℃/min of heating rate, at 180 ℃ of thermal reduction 10h, then naturally cools to room temperature, and the blue film in copper belt surface is transformed into wine-colored Cu nano-wire array.Gained sample carries out surface sweeping Electronic Speculum (SEM) and characterizes, and as shown in Figure 9, the nano-wire array of homogeneous is grown in the substrate of copper belt copper, obtains three-dimensional Arrays of Copper Nanowires collector for lithium ion battery.
4, Electrochemical Characterization test:
Above-mentioned lithium ion battery is used for to load lithium ion battery anode material with three-dimensional Arrays of Copper Nanowires collector, at collection liquid surface electro-deposition layer of metal tin (Sn) film.Electrodeposition condition: plating solution is 0.05M SnSO 4with 1.5M H 2sO 4mixed solution, the saturated calogreen electrode of constant potential-1.0V(is reference electrode), sedimentation time 30 S.
In contrast, at the bright direct electro-deposition one deck Sn film in copper belt surface.Electrodeposition condition: plating solution is 0.05M SnSO 4with 1.5M H 2sO 4mixed solution, the saturated calogreen electrode of constant potential-1.0V(is reference electrode), sedimentation time 120 S.
Have the copper belt of Sn film to be cut into the sequin that diameter is about 14 mm electro-deposition, directly, as the positive pole of lithium ion battery, metal lithium sheet is as negative pole, and electrolyte is by LiPF 6, ethylene carbonate and diethyl carbonate form (LiPF in electrolyte 6concentration is 1M, and the volume ratio of ethylene carbonate and diethyl carbonate is 1:1), barrier film is Celgard2400 microporous polypropylene membrane, is assembled into 2025 type button cells in being full of the glove box of argon gas.
2025 type button cells are carried out to charge-discharge test, and lithium ion battery is 1336.2 mAh/g by the discharge capacity first of three-dimensional Arrays of Copper Nanowires collector base Sn film, and the capacity after 30 times that circulates is 440.5mAh/g, and capability retention is 40.1%; The discharge capacity first of red copper tape base Sn film of light is 1288.9mAh/g, and the capacity after 30 times that circulates is 210.4 mAh/g, and capability retention is 21.1%.Obviously, lithium ion battery has better charge-discharge performance with three-dimensional Arrays of Copper Nanowires collector for load lithium ion battery negative material Sn film.
Embodiment tri-:
1, the copper belt of 1.5 * 1.5 cm is first removed to the oxide on copper surface for 4 minutes with the hydrochloric acid solution immersion of 2M, then with distilled water, clean 5 times, then clean 3 times with ethanol, dry rear standby; Configuration concentration is KOH solution or the NaOH solution for standby of 0.1M.
2, take copper belt as anode, 304 stainless steel substrates are negative electrode, and saturated calogreen electrode is reference electrode, the about 3cm of anode and cathode spacing, and the KOH solution of 0.1M or NaOH solution are electrolyte, at 60 ℃, first in electrolysis tank, pass into inert gas (high-purity N 2or Ar 2deng) approximately 30 min are except O 2, then control constant current density 0.5 mA/cm 2, anodic oxidation times 30 min, at the Cu of copper belt Surface Creation blueness (OH) 2film, cleans 3 times dry for standby with distilled water.
3, by the blue Cu (OH) of Surface Creation 2the copper belt of film is put into reactor---and tubular sealed stove, passes into the H being produced by hydrogen generator 2, 3 ℃/min of heating rate, at 160 ℃ of thermal reduction 20h, then naturally cools to room temperature, and the blue film in copper belt surface is transformed into wine-colored Cu nano-wire array.Gained sample carries out surface sweeping Electronic Speculum (SEM) and characterizes, and as shown in figure 10, the nano-wire array of homogeneous is grown in the substrate of copper belt copper, obtains three-dimensional Arrays of Copper Nanowires collector for lithium ion battery.
4, Electrochemical Characterization test:
Above-mentioned lithium ion battery is used for to load lithium ion battery anode material with three-dimensional Arrays of Copper Nanowires collector, at collection liquid surface electro-deposition layer of metal tin (Sn) film.Electrodeposition condition: plating solution is 0.05M SnSO 4with 1.5M H 2sO 4mixed solution, the saturated calogreen electrode of constant potential-1.0V(is reference electrode), sedimentation time 30 S.
In contrast, at the bright direct electro-deposition one deck Sn film in copper belt surface.Electrodeposition condition: plating solution is 0.05M SnSO 4with 1.5M H 2sO 4mixed solution, the saturated calogreen electrode of constant potential-1.0V(is reference electrode), sedimentation time 120 S.
Have the copper belt of Sn film to be cut into the sequin that diameter is about 14 mm electro-deposition, directly, as the positive pole of lithium ion battery, metal lithium sheet is as negative pole, and electrolyte is by LiPF 6, ethylene carbonate and diethyl carbonate form (LiPF in electrolyte 6concentration is 1M, and the volume ratio of ethylene carbonate and diethyl carbonate is 1:1), barrier film is Celgard2400 microporous polypropylene membrane, is assembled into 2025 type button cells in being full of the glove box of argon gas.
2025 type button cells are carried out to charge-discharge test, and lithium ion battery is 1338.5 mAh/g by the discharge capacity first of three-dimensional Arrays of Copper Nanowires collector base Sn film, and the capacity after 30 times that circulates is 442.3.5mAh/g, and capability retention is 40.6%; The discharge capacity first of red copper tape base Sn film of light is 1289.6mAh/g, and the capacity after 30 times that circulates is 211.8 mAh/g, and capability retention is 21.8%.Obviously, lithium ion battery has better charge-discharge performance with three-dimensional Arrays of Copper Nanowires collector for load lithium ion battery negative material Sn film.
Embodiment tetra-:
1, the copper belt of 1.5 * 1.5 cm is first removed to the oxide on copper surface for 4 minutes with the hydrochloric acid solution immersion of 1.5M, then with distilled water, clean 5 times, then clean 3 times with ethanol, dry rear standby; Configuration concentration is KOH solution or the NaOH solution for standby of 4M.
2, take copper belt as anode, 304 stainless steel substrates are negative electrode, and saturated calogreen electrode is reference electrode, the about 3cm of anode and cathode spacing, and the KOH solution of 4M or NaOH solution are electrolyte, at 5 ℃, first in electrolysis tank, pass into inert gas (high-purity N 2or Ar 2deng) approximately 30 min are except O 2, then control constant current density 5 mA/cm 2, anodic oxidation times 4 min, at the Cu of copper belt Surface Creation blueness (OH) 2film, cleans 3 times dry for standby with distilled water.
3, by the blue Cu (OH) of Surface Creation 2the copper belt of film is put into reactor---and tubular sealed stove, passes into the H being produced by hydrogen generator 2, 3 ℃/min of heating rate, at 200 ℃ of thermal reduction 15h, then naturally cools to room temperature, and the blue film in copper belt surface is transformed into wine-colored Cu nano-wire array.Gained sample carries out surface sweeping Electronic Speculum (SEM) and characterizes, and as shown in figure 11, the nano-wire array of homogeneous is grown in the substrate of copper belt copper, obtains three-dimensional Arrays of Copper Nanowires collector for lithium ion battery.
4, Electrochemical Characterization test:
Above-mentioned lithium ion battery is used for to load lithium ion battery anode material with three-dimensional Arrays of Copper Nanowires collector, at collection liquid surface electro-deposition layer of metal tin (Sn) film.Electrodeposition condition: plating solution is 0.05M SnSO 4with 1.5M H 2sO 4mixed solution, the saturated calogreen electrode of constant potential-1.0V(is reference electrode), sedimentation time 30 S.
In contrast, at the bright direct electro-deposition one deck Sn film in copper belt surface.Electrodeposition condition: plating solution is 0.05M SnSO 4with 1.5M H 2sO 4mixed solution, the saturated calogreen electrode of constant potential-1.0V(is reference electrode), sedimentation time 120 S.
Have the copper belt of Sn film to be cut into the sequin that diameter is about 14 mm electro-deposition, directly, as the positive pole of lithium ion battery, metal lithium sheet is as negative pole, and electrolyte is by LiPF 6, ethylene carbonate and diethyl carbonate form (LiPF in electrolyte 6concentration is 1M, and the volume ratio of ethylene carbonate and diethyl carbonate is 1:1), barrier film is Celgard2400 microporous polypropylene membrane, is assembled into 2025 type button cells in being full of the glove box of argon gas.
2025 type button cells are carried out to charge-discharge test, and lithium ion battery is 1337.9 mAh/g by the discharge capacity first of three-dimensional Arrays of Copper Nanowires collector base Sn film, and the capacity after 30 times that circulates is 442.3mAh/g, and capability retention is 40.7%; The discharge capacity first of red copper tape base Sn film of light is 1289.6mAh/g, and the capacity after 30 times that circulates is 211.5 mAh/g, and capability retention is 20.9%.Obviously, lithium ion battery has better charge-discharge performance with three-dimensional Arrays of Copper Nanowires collector for load lithium ion battery negative material Sn film.
When preparing lithium ion battery with three-dimensional Arrays of Copper Nanowires collector, following condition combination in any can be used: concentration of hydrochloric acid is 0.1~2 mol/L, and electrolyzer temperature is 5~60 ℃ of scopes, and the concentration of electrolyte is 0.1~4 mol/L; Constant current density is 0.5~5 mA/cm 2, the anodic oxidation time is 4~30 min; H 2the temperature of thermal reduction is 160~200 ℃, and the time is 10~20h.
Except technical characterictic described in specification, all the other technical characterictics are those skilled in the art's known technology.

Claims (6)

1. a three-dimensional Arrays of Copper Nanowires collector for lithium ion battery, is characterized in that: it is comprised of the Arrays of Copper Nanowires that is grown directly upon copper surface.
2. prepare a method for three-dimensional Arrays of Copper Nanowires collector for lithium ion battery claimed in claim 1, it is characterized in that, step is as follows:
1) take red copper as anode, NaOH (NaOH) solution or potassium hydroxide (KOH) solution are electrolyte, and stainless steel is negative electrode, and saturated calogreen electrode is reference electrode, first in electrolysis tank, pass into inert gas and remove oxygen (O within the scope of 5~60 ℃ 2), then controlling current density is 0.5~5 mA/cm 2, anodic oxidation 4~30 min, generate blue Cu (OH) at red copper surface 2film, cleans and dries with distilled water, obtains Cu (OH) 2nano-wire array;
2) by Cu (OH) 2nano-wire array is placed in nitrogen atmosphere, in the reactor of 160~200 ℃, and thermal reduction 10~20h, then naturally cool to room temperature, can obtain three-dimensional copper nano-wire battle array collector.
3. the preparation method of three-dimensional Arrays of Copper Nanowires collector for lithium ion battery according to claim 2, it is characterized in that, the hydrochloric acid of first red copper being put into 0.1~2mol/L soaks 3~5min, then with distilled water, cleans, with ethanol, clean again, dry rear standby.
4. the preparation method with three-dimensional Arrays of Copper Nanowires collector according to the lithium ion battery described in claim 2 or 3, is characterized in that, the concentration of described NaOH (NaOH) solution or potassium hydroxide (KOH) solution is 0.1~4mol/L.
5. the preparation method of three-dimensional Arrays of Copper Nanowires collector for lithium ion battery according to claim 4, is characterized in that, described inert gas is high-purity N 2or Ar 2.
6. the preparation method of three-dimensional Arrays of Copper Nanowires collector for lithium ion battery according to claim 5, is characterized in that, described hydrogen is produced by hydrogen generator.
CN201310488208.8A 2013-10-17 2013-10-17 Three-dimensional copper nanowire array current collector for lithium ion battery and production method of three-dimensional copper nanowire array current collector Pending CN103531817A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310488208.8A CN103531817A (en) 2013-10-17 2013-10-17 Three-dimensional copper nanowire array current collector for lithium ion battery and production method of three-dimensional copper nanowire array current collector

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310488208.8A CN103531817A (en) 2013-10-17 2013-10-17 Three-dimensional copper nanowire array current collector for lithium ion battery and production method of three-dimensional copper nanowire array current collector

Publications (1)

Publication Number Publication Date
CN103531817A true CN103531817A (en) 2014-01-22

Family

ID=49933649

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310488208.8A Pending CN103531817A (en) 2013-10-17 2013-10-17 Three-dimensional copper nanowire array current collector for lithium ion battery and production method of three-dimensional copper nanowire array current collector

Country Status (1)

Country Link
CN (1) CN103531817A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104617307A (en) * 2015-01-29 2015-05-13 北京化工大学 Electrode material with surface nanometer-micrometer structure, preparation method thereof and hydrazine hydrate fuel battery containing electrode material
CN105641973A (en) * 2016-01-25 2016-06-08 四川大学 Preparation method of nano-structure oil-water separation net membrane with self-cleaning and underwater super-oleophobic characteristics
CN105938762A (en) * 2016-07-12 2016-09-14 安徽大学 Method for preparing flexible solid super capacitor based on linear Cu(OH)2@NiCo2O4 multilevel nano array
CN105990044A (en) * 2016-01-20 2016-10-05 安徽大学 Preparation method for flexible solid supercapacitor Cu(OH)2@Ni2(OH)2CO3 multistage nanoarray electrodes
CN106989619A (en) * 2017-04-01 2017-07-28 深圳万智联合科技有限公司 A kind of radiator based on polyaniline composite armor
CN108075142A (en) * 2016-11-17 2018-05-25 中国科学院大连化学物理研究所 A kind of preparation method for anion-exchange membrane fuel cells nano-array Catalytic Layer
CN108428858A (en) * 2018-04-12 2018-08-21 清华大学深圳研究生院 A kind of lithium an- ode of stabilization
CN108666579A (en) * 2017-03-28 2018-10-16 通用汽车环球科技运作有限责任公司 The electrode of lithium cell of copper foil current collector is modified using surface
CN110492087A (en) * 2019-09-10 2019-11-22 中南大学 A kind of method of modifying of in-stiu coating anode material for lithium-ion batteries
CN111403678A (en) * 2020-01-17 2020-07-10 华中科技大学 Three-dimensional flexible metal cathode and preparation method thereof
CN112349875A (en) * 2020-10-23 2021-02-09 四川大学 Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429680A (en) * 2008-08-01 2009-05-13 华中师范大学 Production method for direct growth of one-dimensional nano cuprous oxide array on metallic copper substrate
CN102602978A (en) * 2012-03-22 2012-07-25 哈尔滨工业大学 Preparation method of CuO micro-/nano-array electrode for lithium ion battery
CN103265061A (en) * 2013-04-23 2013-08-28 北京化工大学 One-dimensional copper oxide nano-array glucose sensor electrode material and preparation method thereof
CN104959045A (en) * 2015-06-16 2015-10-07 陕西科技大学 Method for manufacturing polyvinylidene fluoride nano array pore membranes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429680A (en) * 2008-08-01 2009-05-13 华中师范大学 Production method for direct growth of one-dimensional nano cuprous oxide array on metallic copper substrate
CN102602978A (en) * 2012-03-22 2012-07-25 哈尔滨工业大学 Preparation method of CuO micro-/nano-array electrode for lithium ion battery
CN103265061A (en) * 2013-04-23 2013-08-28 北京化工大学 One-dimensional copper oxide nano-array glucose sensor electrode material and preparation method thereof
CN104959045A (en) * 2015-06-16 2015-10-07 陕西科技大学 Method for manufacturing polyvinylidene fluoride nano array pore membranes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DAVID REYTER ET AL: "An electrochemically roughened Cu current collector for Si-based electrode in Li-ion batteries", 《JOURNAL OF POWER SOURCES》, vol. 239, 2 April 2013 (2013-04-02), pages 309 - 2, XP028566932, DOI: 10.1016/j.jpowsour.2013.03.108 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104617307A (en) * 2015-01-29 2015-05-13 北京化工大学 Electrode material with surface nanometer-micrometer structure, preparation method thereof and hydrazine hydrate fuel battery containing electrode material
CN105990044A (en) * 2016-01-20 2016-10-05 安徽大学 Preparation method for flexible solid supercapacitor Cu(OH)2@Ni2(OH)2CO3 multistage nanoarray electrodes
CN105641973A (en) * 2016-01-25 2016-06-08 四川大学 Preparation method of nano-structure oil-water separation net membrane with self-cleaning and underwater super-oleophobic characteristics
CN105938762A (en) * 2016-07-12 2016-09-14 安徽大学 Method for preparing flexible solid super capacitor based on linear Cu(OH)2@NiCo2O4 multilevel nano array
CN108075142B (en) * 2016-11-17 2020-03-10 中国科学院大连化学物理研究所 Preparation method of nano-array catalyst layer for anion exchange membrane fuel cell
CN108075142A (en) * 2016-11-17 2018-05-25 中国科学院大连化学物理研究所 A kind of preparation method for anion-exchange membrane fuel cells nano-array Catalytic Layer
CN108666579A (en) * 2017-03-28 2018-10-16 通用汽车环球科技运作有限责任公司 The electrode of lithium cell of copper foil current collector is modified using surface
CN106989619A (en) * 2017-04-01 2017-07-28 深圳万智联合科技有限公司 A kind of radiator based on polyaniline composite armor
CN108428858A (en) * 2018-04-12 2018-08-21 清华大学深圳研究生院 A kind of lithium an- ode of stabilization
CN110492087A (en) * 2019-09-10 2019-11-22 中南大学 A kind of method of modifying of in-stiu coating anode material for lithium-ion batteries
CN111403678A (en) * 2020-01-17 2020-07-10 华中科技大学 Three-dimensional flexible metal cathode and preparation method thereof
CN111403678B (en) * 2020-01-17 2021-07-27 华中科技大学 Three-dimensional flexible metal cathode and preparation method thereof
CN112349875A (en) * 2020-10-23 2021-02-09 四川大学 Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method
CN112349875B (en) * 2020-10-23 2021-08-10 四川大学 Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method

Similar Documents

Publication Publication Date Title
CN103531817A (en) Three-dimensional copper nanowire array current collector for lithium ion battery and production method of three-dimensional copper nanowire array current collector
CN106654221B (en) Three-dimensional porous carbon coating selenizing Zinc material and preparation method thereof for negative electrode of lithium ion battery
CN104617271B (en) Stannic selenide/graphene oxide negative pole composite material for sodium ion battery and preparation method thereof
CN102394305B (en) Foamy copper oxide/copper lithium ion battery anode and preparation method thereof
CN105655152A (en) Ni-Mn layered double hydroxide@nickel foam@carbon three-dimensional hierarchically-structured electrode material and preparation method thereof
Chen et al. Facile fabrication of CuO 1D pine-needle-like arrays for super-rate lithium storage
CN102602978B (en) Preparation method of CuO micro-/nano-array electrode for lithium ion battery
CN105789584A (en) Cobalt selenide/carbon sodium ion battery composite negative electrode material as well as preparation method and application of cobalt selenide/carbon-sodium ion battery composite negative electrode material
CN105789690A (en) Rechargeable magnesium battery and preparation method thereof
CN109004199B (en) Preparation method of biomass hard carbon material for negative electrode of sodium-ion battery
CN105633360B (en) Amorphous state ferroso-ferric oxide/graphene aerogel composite, preparation method and applications
CN105810922B (en) A kind of lithium ion/sodium-ion battery composite negative pole material and preparation method thereof
CN109167035A (en) Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation
CN108461706A (en) The preparation method of photonic crystal lithium-sulfur cell based on metal ordered porous structural
Cao et al. NiO nanowall array prepared by a hydrothermal synthesis method and its enhanced electrochemical performance for lithium ion batteries
CN109786670A (en) A kind of preparation method of the negative electrode of lithium ionic secondary battery of Gao Shouxiao
CN107342421B (en) High-content pyridine nitrogen-doped porous carbon negative electrode material, and preparation method and application thereof
CN103500836A (en) Roughened copper-foil current collector for lithium ion battery and method for manufacturing roughened copper-foil current collector
CN108364806A (en) A kind of tree-shaped three-dimensional structure metal material and preparation method thereof and application in the battery
CN108199003A (en) A kind of big/mesoporous antimony cathode of three-dimensional, preparation method and applications
CN108039514A (en) A kind of electroplating preparation method of the lithium ion battery with reference electrode
Tan et al. Fabrication of an all-solid-state Zn-air battery using electroplated Zn on carbon paper and KOH-ZrO2 solid electrolyte
CN103400980A (en) Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof
CN109273672B (en) Na-K liquid alloy electrode coated with in-situ SEI film as well as preparation method and application thereof
Jiang et al. In situ growth of CuO submicro-sheets on optimized Cu foam to induce uniform Li deposition and stripping for stable Li metal batteries

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
C41 Transfer of patent application or patent right or utility model
TA01 Transfer of patent application right

Effective date of registration: 20141126

Address after: 274000 Changjiang Road, Heze Development Zone, Shandong, China, No. 4666

Applicant after: Jade Emperor flourishing age chemical inc, Shandong

Address before: 274500 Shandong city of Heze province Dongming County wusheng Development Zone

Applicant before: Shandong Yuhuang Chemical Co., Ltd.

ASS Succession or assignment of patent right

Owner name: SHANDONG YUHUANG SHENGSHI CHEMICAL CO., LTD.

Free format text: FORMER OWNER: SHANDONG YUHUANG CHEMICAL CO., LTD.

Effective date: 20141126

COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 274500 HEZE, SHANDONG PROVINCE TO: 274000 HEZE, SHANDONG PROVINCE

RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20140122