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 PDFInfo
- 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
Links
Images
Classifications
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/044—Activating, forming or electrochemical attack of the supporting material
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
-
- 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
-
- 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 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
(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:
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.
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 (17)
| 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 |
| CN108395565A (en) * | 2018-05-02 | 2018-08-14 | 清华大学深圳研究生院 | A kind of preparation method of nanoporous SEBS films |
| 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 |
| CN113322490A (en) * | 2020-02-28 | 2021-08-31 | 天津大学 | In-situ synthesized copper nanowire array material and preparation method and application thereof |
| CN113862754A (en) * | 2020-06-30 | 2021-12-31 | 南京理工大学 | Preparation method of green pause-sensing nano-array initiating explosive |
| CN114094115A (en) * | 2021-10-13 | 2022-02-25 | 中国长江三峡集团有限公司 | Columnar copper array current collector and preparation method and application thereof |
| CN114300280A (en) * | 2021-12-13 | 2022-04-08 | 山东黄海科技创新研究院有限责任公司 | Preparation method of electrode material |
| CN114864292A (en) * | 2022-04-21 | 2022-08-05 | 华南理工大学 | Composite electrode material and preparation method and application thereof |
Citations (4)
| 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 |
-
2013
- 2013-10-17 CN CN201310488208.8A patent/CN103531817A/en active Pending
Patent Citations (4)
| 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)
| 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 (25)
| 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 |
| CN108666579B (en) * | 2017-03-28 | 2022-01-14 | 通用汽车环球科技运作有限责任公司 | Lithium battery electrode using surface modified copper foil current collector |
| 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 |
| US11427914B2 (en) | 2017-03-28 | 2022-08-30 | GM Global Technology Operations LLC | Lithium cell electrode using surface-modified copper foil current collector |
| 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 |
| CN108395565A (en) * | 2018-05-02 | 2018-08-14 | 清华大学深圳研究生院 | A kind of preparation method of nanoporous SEBS films |
| CN108395565B (en) * | 2018-05-02 | 2023-06-16 | 清华大学深圳研究生院 | Preparation method of nano porous SEBS film |
| 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 |
| CN113322490A (en) * | 2020-02-28 | 2021-08-31 | 天津大学 | In-situ synthesized copper nanowire array material and preparation method and application thereof |
| CN113322490B (en) * | 2020-02-28 | 2022-05-24 | 天津大学 | In-situ synthesized copper nanowire array material and preparation method and application thereof |
| CN113862754A (en) * | 2020-06-30 | 2021-12-31 | 南京理工大学 | Preparation method of green pause-sensing nano-array initiating explosive |
| CN113862754B (en) * | 2020-06-30 | 2024-02-13 | 南京理工大学 | Preparation method of green ton sense nano array initiating explosive |
| 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 |
| CN114094115A (en) * | 2021-10-13 | 2022-02-25 | 中国长江三峡集团有限公司 | Columnar copper array current collector and preparation method and application thereof |
| CN114300280A (en) * | 2021-12-13 | 2022-04-08 | 山东黄海科技创新研究院有限责任公司 | Preparation method of electrode material |
| CN114864292A (en) * | 2022-04-21 | 2022-08-05 | 华南理工大学 | Composite electrode material and preparation method and application thereof |
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 | |
| CN114050246B (en) | Micron-sized porous sodium ferrous sulfate/carbon composite cathode material and sodium ion battery or sodium battery prepared from same | |
| 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 | |
| Chen et al. | Facile fabrication of CuO 1D pine-needle-like arrays for super-rate lithium storage | |
| 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 | |
| CN109786670A (en) | A kind of preparation method of the negative electrode of lithium ionic secondary battery of Gao Shouxiao | |
| 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 | |
| CN109167035A (en) | Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation | |
| CN105655152A (en) | Ni-Mn layered double hydroxide@nickel foam@carbon three-dimensional hierarchically-structured electrode material and preparation method thereof | |
| CN110416529B (en) | Flexible zinc negative electrode material and preparation method and application thereof | |
| CN110350200A (en) | A kind of lithium ion battery three-dimensional Arrays of Copper Nanowires collector and preparation method thereof | |
| CN107342421B (en) | High-content pyridine nitrogen-doped porous carbon negative electrode material, and preparation method and application thereof | |
| CN105633360B (en) | Amorphous state ferroso-ferric oxide/graphene aerogel composite, preparation method and applications | |
| CN111952572A (en) | Cobalt-nickel bimetallic nitrogen-doped carbon composite material containing single-atom active site and preparation method and application thereof | |
| CN105810922B (en) | A kind of lithium ion/sodium-ion battery composite negative pole material and preparation method thereof | |
| Tan et al. | Fabrication of an all-solid-state Zn-air battery using electroplated Zn on carbon paper and KOH-ZrO2 solid electrolyte | |
| 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 | |
| CN109273672B (en) | Na-K liquid alloy electrode coated with in-situ SEI film as well as preparation method and application thereof | |
| CN111048750A (en) | Graphene aerogel/metallic lithium composite negative electrode material and preparation method thereof | |
| CN109301255A (en) | A kind of 3D porous current collector and its preparation method and application | |
| CN112331933A (en) | Long-cycle-life cathode of aqueous zinc secondary battery and preparation and application thereof | |
| CN108364806A (en) | A kind of tree-shaped three-dimensional structure metal material and preparation method thereof and application in the battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| 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 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 274500 HEZE, SHANDONG PROVINCE TO: 274000 HEZE, SHANDONG PROVINCE |
|
| 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. |
|
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140122 |
|
| RJ01 | Rejection of invention patent application after publication |