CN106229462B - The cuprous nano-chip arrays type negative electrode of lithium ion battery of three-D nano-porous copper/two dimensional oxidation and one one-step preparation method - Google Patents

The cuprous nano-chip arrays type negative electrode of lithium ion battery of three-D nano-porous copper/two dimensional oxidation and one one-step preparation method Download PDF

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CN106229462B
CN106229462B CN201610620678.9A CN201610620678A CN106229462B CN 106229462 B CN106229462 B CN 106229462B CN 201610620678 A CN201610620678 A CN 201610620678A CN 106229462 B CN106229462 B CN 106229462B
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nano
ion battery
lithium ion
cuprous
negative electrode
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CN106229462A (en
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刘文博
陈龙
李宁
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Sichuan University
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Sichuan University
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    • 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
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • 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
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1395Processes of manufacture of electrodes based on metals, Si or alloys
    • 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 present invention provides a kind of three-D nano-porous cuprous nano-chip arrays type negative electrode of lithium ion battery of copper/two dimensional oxidation, the negative electrode of lithium ion battery is made of three-D nano-porous copper base and cuprous nano array layers, using three-D nano-porous copper base as collector, it is activity storage lithium layer with cuprous nano array layers, cuprous nano array layers are located at the substrate surface and are combined as a whole with substrate, cuprous nano array layers are made of the cuprous nano piece of growth in situ on the substrate, cuprous nano piece is perpendicular to three-D nano-porous copper base and is staggered to form array structure, the negative electrode of lithium ion battery can improve the cycle performance and specific capacity of lithium ion battery.The present invention also provides an a kind of one-step preparation method of above-mentioned negative electrode of lithium ion battery, this method can effectively simplify the production technology of negative electrode of lithium ion battery.

Description

The three-D nano-porous cuprous nano-chip arrays type lithium ion battery of copper/two dimensional oxidation is negative Pole and one one-step preparation method
Technical field
The invention belongs to negative electrode of lithium ion battery field, in particular to a kind of negative electrode of lithium ion battery and preparation method thereof.
Background technique
Currently, the negative electrode material of commercial Li-ion battery is generally graphite, although graphite stable structure, followed in charge and discharge There is stable reversible capacity, but shortcoming is that its theoretical specific capacity only has 372mAh/g in ring, it is difficult to meet quick at present The electronic equipment of development requires the higher energy density of lithium ion battery, meanwhile, New Generation of Electric Vehicle and hybrid power vapour The commercialized development of vehicle, higher requirements are also raised for energy density and performance to lithium ion battery, therefore has higher ratio The novel cathode of capacity is the research hotspot of current field of lithium.
Dequan Liu et al. is disclosed using nickel foam as the nano porous copper of collector/cuprous oxide membranous type lithium ion battery The preparation method (see Nanoscale, 2013,5,1917-1921.) of cathode, this method is by Cu50Al50Alloy is placed in 60 DEG C of hydrogen Immersion prepares nano porous copper in sodium hydroxide solution, and powdery is made simultaneously in nano porous copper and polyvinylidene fluoride is according to 9:1's Mass ratio mixes in the case where a small amount of N-Methyl pyrrolidone is added and forms slurry, and gained slurry is coated in nickel foam afflux On body and under vacuum conditions in 120 DEG C of dry 10h, then in air in 140 DEG C of heating 3min i.e. in nano porous copper It is formed on wall surface of the hole with a thickness of 15~20nm cuprous oxide film, obtains negative electrode of lithium ion battery.This method and its lithium of preparation from Sub- battery cathode has the disadvantage that (1) this method needs first to prepare nano porous copper, then cooperates binder and solvent modulation Slurry is simultaneously coated in foamed nickel current collector, and re-dry and heated oxide form cuprous oxide in the wall surface of the hole of nano porous copper Film, operating procedure is more, complex production process;(2) it due to having used binder during preparing negative electrode of lithium ion battery, glues Knot agent itself is non-conductive and cannot contribute capacity, will lead to that electronics conduction is obstructed and specific capacity reduces;(3) structure of the cathode Complexity, cuprous oxide film is located at the wall surface of the hole of nano porous copper, and nano porous copper is bonded in foam nickel surface, and electronics is transmitted to The path of collector is longer, in addition the obstruction of binder, and this structure seriously can hinder electronics to conduct, cause lithium ion battery Cycle performance reduces;(4) cuprous oxide is covered in membrane form on the wall surface of the hole of nano porous copper, and the oxidation of this structure is sub- The specific surface area of copper is relatively small, is effectively improved so that cuprous oxide is unable to get as the electric conductivity of semiconductor, this is not yet Conducive to electronics conduction, electronics conduction be obstructed will lead to lithium ion battery cycle performance it is bad.
Summary of the invention
It is sub- that it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of three-D nano-porous copper/two dimensional oxidations Copper nano-chip arrays type negative electrode of lithium ion battery and one one-step preparation method, to improve the cycle performance and specific volume of lithium ion battery Amount simplifies the production technology of negative electrode of lithium ion battery.
The cuprous nano-chip arrays type negative electrode of lithium ion battery of three-D nano-porous copper/two dimensional oxidation provided by the invention, by Three-D nano-porous copper base and cuprous nano array layers composition, using three-D nano-porous copper base as collector, with Cuprous nano array layers are activity storage lithium layer, and cuprous nano array layers are located at the substrate surface and and substrate It is combined as a whole, cuprous nano array layers are made of the cuprous nano piece of growth in situ on the substrate.
In the cuprous nano array layers of above-mentioned negative electrode of lithium ion battery, cuprous nano piece is perpendicular to three wieners Meter Duo Kong copper base and be staggered to form array structure, cuprous nano array layers with a thickness of 50nm~1.0 μm.
In above-mentioned negative electrode of lithium ion battery, it is characterised in that the cuprous nano piece with a thickness of 2nm~60nm, oxygen The width for changing cuprous nanometer sheet is 50nm~500nm, length is 100nm~1.5 μm.The width and length of cuprous nano piece Respectively represent the side length of most short side and the side length of longest edge in each cuprous nano piece.
In above-mentioned negative electrode of lithium ion battery, the pore-size of the three-D nano-porous copper base is 30nm~60nm, three Tie up nano porous copper substrate with a thickness of 0.1mm~0.6mm.
In above-mentioned negative electrode of lithium ion battery, cuprous nano piece growth in situ refers on three-D nano-porous copper base Cuprous nano piece is grown directly upon the substrate surface.
Above-mentioned negative electrode of lithium ion battery provided by the invention is in use, without adding any binder and conductive agent, directly Connect working electrode using the negative electrode of lithium ion battery as lithium ion battery, using metal lithium sheet or lithium source material as to electrode, Lithium-ion electric is assembled into full of argon gas and water content and oxygen content glove box up to standard using suitable electrolyte and diaphragm Pond.
The present invention also provides a kind of above-mentioned three-D nano-porous cuprous nano-chip arrays type lithium-ion electrics of copper/two dimensional oxidation One one-step preparation method of pond cathode operates as follows:
By cupromanganese piece sanding and polishing, is then cleaned and dried with ethyl alcohol or acetone, with the cupromanganese piece after drying As working electrode, using saturated calomel electrode as reference electrode, using platinum electrode as auxiliary electrode, by working electrode, reference Electrode and auxiliary electrode are placed in corrosive liquid, and the constant potential for applying 0.1V~3.0V to working electrode and auxiliary electrode carries out electricity Chemical attack, corrosion form negative electrode of lithium ion battery when bubble-free generates into corrosive liquid, negative electrode of lithium ion battery are taken out Cleaning removal corrosive liquid, then in 45 DEG C~75 DEG C dryings and be cooled to room temperature under vacuum conditions;
The corrosive liquid is the sulfuric acid solution that concentration is 1wt.%~50wt.%, the oxygen concentration in corrosive liquid be 8mg/L~ The dosage of 10mg/L, corrosive liquid should at least flood working electrode completely.
In the above method, the atomic percent of copper is 10%~80% in the cupromanganese piece, the atomic percent of manganese It is 90%~20%, cupromanganese piece is cast by purity >=99.9wt.% copper and manganese.In order to reach production lithium-ion electric The intensity requirement of pond cathode, the thickness of cupromanganese piece are preferably 0.1mm~0.6mm, the specific size of cupromanganese piece according to Practical application request is determined.
In the above method, when corrosive liquid on cleaning removal negative electrode of lithium ion battery, successively with deionized water and ethyl alcohol into Row cleaning.
In the above method, under vacuum conditions in 45 DEG C~75 DEG C be dried be in order to avoid it is dry when lithium ion battery Cuprous nano piece in cathode is oxidized, and preferred drying time is 10h~36h.
In the above method, in order in three-D nano-porous copper base surface formation cuprous nano piece, corrosive liquid Oxygen concentration is 8~10mg/L, due in normal pressure, under room temperature, oxygen solubility of solution in aqueous phase solution is about 8~ 10mg/L, therefore the corrosive liquid that oxygen concentration is 8mg/L~10mg/L can be obtained after the concentrated sulfuric acid is diluted with deionized water.
The principle of the method for the invention is as follows: in corrosive liquid, the higher manganese atom of activity can be excellent in cupromanganese piece First by selective corrosion, causes a large amount of copper atom to be exposed, be not coordinated around the copper atom being exposed due to these Atom or coordination atom are seldom, therefore these copper atoms have the mobility of height, can to diffusion aggregation around at metal cluster, with Manganese atom corrosion and copper atom reunite progress, cupromanganese on piece formed pit can penetrate entire cupromanganese piece simultaneously Ultimately form three-D nano-porous copper base.And electrochemical means are used, by applying constant potential, not only three-dimensional manometer can be made more The formation speed of hole steel structure is accelerated, and is able to achieve the controllability of nano-pore structure;Simultaneously as the exposure in corrosion process There is no coordination atom or coordination atom seldom around copper atom out, they can be in conjunction with the oxygen in corrosive liquid, but this is also insufficient To form cuprous oxide, the constant potential applied can increase a driving force to the combination of copper atom and oxygen, thus in three wieners The surface of meter Duo Kong copper base is formed in cuprous nano array layers and the cuprous nano array layers, cuprous oxide Nanometer sheet is perpendicular to three-D nano-porous copper base and is staggered to form array structure.
Compared with prior art, the invention has the following advantages:
1. the negative electrode of lithium ion battery is by three-dimensional manometer the present invention provides a kind of new structural negative electrode of lithium ion battery Porous copper base and cuprous nano array layers composition, three-D nano-porous copper base are received as collector and cuprous oxide Rice array layers carrier, cuprous nano chip arrays as activity storage lithium layer, three-D nano-porous copper as collector not Only there is excellent electric conductivity, and volume change of the cuprous oxide in charge and discharge process can be alleviated to a certain extent, from And the cycle performance of lithium ion battery is improved, meanwhile, in cuprous nano array layers, cuprous nano piece is perpendicular to three Dimension and is staggered to form array structure at nano porous copper substrate, which has high reference area, this can be improved lithium from The electrolyte of sub- battery and the contact area of cuprous oxide, so that cuprous oxide is effectively changed as the electric conductivity of semiconductor Kind, high specific surface area also can be shortened electronics conduction distance, improves electronics conduction of velocity, is conducive to cycle performance of lithium ion battery Raising.
2. without binder and directly with three-D nano-porous copper base work in negative electrode of lithium ion battery provided by the invention For collector, this not only can largely reduce the internal resistance of lithium ion battery, promote electronics conduction, improve lithium ion battery Electric conductivity, and can effectively shorten electrical conductance path, above-mentioned factor is also beneficial to the raising of cycle performance of lithium ion battery.
3. experiment shows that the lithium ion battery being assembled into negative electrode of lithium ion battery provided by the invention and lithium piece exists 0.1mA/cm2Current density under first discharge specific capacity be 2.4~3.2mAh/cm2, capacity is maintained at after recycling 150 times 2.1~2.8mAh/cm2, first discharge specific capacity with higher and good cycle charge discharge electrical property.
4. the present invention also provides a kind of new method for preparing negative electrode of lithium ion battery, this method only passes through an one-step electrochemistry Etching operation can form three-D nano-porous copper negative current collector and the load of cuprous nano array layers thereon, nothing Binder need to be used, compared with the production method of existing negative electrode of lithium ion battery, easy to operate, the not only effectively letter of this method The production technology of negative electrode of lithium ion battery is changed, and can be reduced the use of chemical reagent, it is raw to be conducive to negative electrode of lithium ion battery Produce the reduction of cost and the raising of production efficiency.
Detailed description of the invention
Fig. 1 is the XRD curve of negative electrode of lithium ion battery prepared by embodiment 1;
Fig. 2 is the stereoscan photograph on negative electrode of lithium ion battery surface prepared by embodiment 1;
Fig. 3 is that the scanning electron microscope in the three-D nano-porous copper base section of negative electrode of lithium ion battery prepared by embodiment 1 is shone Piece;
Fig. 4 is the cycle performance curve of lithium ion battery prepared by embodiment 1.
Specific embodiment
By the following examples and in conjunction with attached drawing to the three-D nano-porous cuprous nanometer sheet of copper/two dimensional oxidation of the present invention Array type negative electrode of lithium ion battery and one one-step preparation method are described further.
In following each embodiments, the preparation method of corrosive liquid is as follows: in normal pressure, under room temperature, by the dense sulphur of 98wt.% Acid is added in deionized water, stirs evenly the sulfuric acid solution for being configured to respective concentration, it is about 8~10mg/L that oxygen concentration, which can be obtained, Corrosive liquid.
Embodiment 1
In the present embodiment, the system of the three-D nano-porous cuprous nano-chip arrays type negative electrode of lithium ion battery of copper/two dimensional oxidation Preparation Method is as follows:
By copper and manganese atom percentage be 50% cupromanganese block wire cutting machine wire cutting at a thickness of 0.4mm's Cupromanganese piece successively polishes to the surface of cupromanganese piece with the waterproof abrasive paper of 380 mesh, 800 mesh, 1200 mesh, 2000 mesh, Then it is polished with the diamond polishing cream that granularity is 0.5 μm, the cupromanganese piece after polishing is placed in ultrasonic cleaner, used Dehydrated alcohol is cleaned by ultrasonic 2min under the conditions of 100W, takes out simultaneously naturally dry.
Using the cupromanganese piece Jing Guo above-mentioned processing as working electrode, using saturated calomel electrode as reference electrode, with Working electrode, reference electrode and auxiliary electrode are placed in corrosive liquid as auxiliary electrode, utilize electrochemical operation by platinum electrode The constant potential for applying 0.4V to working electrode and auxiliary electrode of standing carries out electrochemical corrosion, corrodes 60min, without gas in corrosive liquid Bubble generates, and completes cuprous nano array layers in the corrosion and three-D nano-porous copper base of cupromanganese piece at this time Load, formed negative electrode of lithium ion battery, gained negative electrode of lithium ion battery is taken out, with deionized water rinse 5 times, use ethyl alcohol again It rinses 5 times, is subsequently placed in vacuum oven, in 65 DEG C of dry 20h and is cooled to room under the conditions of aforementioned vacuum in -0.1MPa Temperature;The corrosive liquid is the sulfuric acid solution that concentration is 5wt.%, and the dosage of corrosive liquid should at least flood working electrode completely.
The XRD curve of negative electrode of lithium ion battery manufactured in the present embodiment as shown in Figure 1, the stereoscan photograph on its surface such as Shown in Fig. 2, the stereoscan photograph in the three-D nano-porous copper base section of the negative electrode of lithium ion battery is as shown in figure 3, by Fig. 1 It is found that the negative electrode of lithium ion battery is made of copper and cuprous oxide, as shown in Figure 2, on the surface of three-D nano-porous copper base Load has cuprous oxide nano-chip arrays layer, by Fig. 2,3 it is found that in cuprous nano array layers, by cuprous nano Piece is perpendicular to three-D nano-porous copper base and is staggered to form array structure, has high specific surface area, and cuprous oxide is received Rice array layers thickness be about 300nm, wherein cuprous nano piece with a thickness of 10nm~30nm, cuprous nano The width of piece is 200nm~350nm, length is 700nm~900nm, and the pore-size of three-D nano-porous copper base is about 40nm。
Negative electrode of lithium ion battery production lithium ion battery manufactured in the present embodiment used below is simultaneously tested for the property.
It is to gather to electrode, using negative electrode of lithium ion battery manufactured in the present embodiment as working electrode, with micropore using metal lithium sheet Propylene is diaphragm, to contain 1M lithium hexafluoro phosphate (LiPF6) ethylene carbonate (EC), dimethyl carbonate (DMC) and carbonic acid two The mixed solution of ethyl ester (DEC) is electrolyte, and in the electrolyte, the volume ratio of EC, DMC and DEC are 1:1:1, full of argon gas, Water and oxygen content, which are below in the glove box of 1ppm, is assembled into lithium ion battery.Using the constant current of model NEWAREBTS-610 Charge and discharge instrument tests obtained lithium ion battery, and current density is 0.1mA/cm when test2, voltage range be 1.5~ 0.1V, test temperature are room temperature.Test result shows in charging and discharging currents density 0.1mA/cm2Under conditions of, the lithium-ion electric The first discharge specific capacity 3.2mAh/cm in pond2, capacity is maintained at 2.6mAh/cm after recycling 150 times2, which follows Ring performance curve is as shown in Figure 4.
Embodiment 2
In the present embodiment, the system of the three-D nano-porous cuprous nano-chip arrays type negative electrode of lithium ion battery of copper/two dimensional oxidation Preparation Method is as follows:
By copper atom percentage is 10%, manganese atom percentage is 90% cupromanganese block wire cutting machine wire cutting at With a thickness of the cupromanganese piece of 0.1mm, successively with 380 mesh, 800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper to cupromanganese piece Surface is polished, and is then polished with the diamond polishing cream that granularity is 0.5 μm, the cupromanganese piece after polishing is placed in ultrasound In wave washer, it is cleaned by ultrasonic 3min under the conditions of 100W with dehydrated alcohol, takes out simultaneously naturally dry.
Using the cupromanganese piece Jing Guo above-mentioned processing as working electrode, using saturated calomel electrode as reference electrode, with Working electrode, reference electrode and auxiliary electrode are placed in corrosive liquid as auxiliary electrode, utilize electrochemical operation by platinum electrode The constant potential for applying 0.1V to working electrode and auxiliary electrode of standing carries out electrochemical corrosion, corrodes 30min, without gas in corrosive liquid Bubble generates, and completes cuprous nano array layers in the corrosion and three-D nano-porous copper base of cupromanganese piece at this time Load, formed negative electrode of lithium ion battery, gained negative electrode of lithium ion battery is taken out, with deionized water rinse 4 times, use ethyl alcohol again It rinses 4 times, is subsequently placed in vacuum oven, -0.1MPa in 45 DEG C of dry 36h and is cooled to room under the conditions of aforementioned vacuum Temperature;The corrosive liquid is the sulfuric acid solution that concentration is 1wt.%, and the dosage of corrosive liquid should at least flood working electrode completely.
Negative electrode of lithium ion battery production lithium ion battery manufactured in the present embodiment used below is simultaneously tested for the property.
It is to gather to electrode, using negative electrode of lithium ion battery manufactured in the present embodiment as working electrode, with micropore using metal lithium sheet Propylene is diaphragm, to contain 1M lithium hexafluoro phosphate (LiPF6) ethylene carbonate (EC), dimethyl carbonate (DMC) and carbonic acid two The mixed solution of ethyl ester (DEC) is electrolyte, and in the electrolyte, the volume ratio of EC, DMC and DEC are 1:1:1, full of argon gas, Water and oxygen content, which are below in the glove box of 1ppm, is assembled into lithium ion battery.Using the constant current of model NEWAREBTS-610 Charge and discharge instrument tests obtained lithium ion battery, and current density is 0.1mA/cm when test2, voltage range be 1.5~ 0.1V, test temperature are room temperature.Test result shows in charging and discharging currents density 0.1mA/cm2Under conditions of, the lithium-ion electric The first discharge specific capacity 2.4mAh/cm in pond2, capacity is maintained at 2.1mAh/cm after recycling 150 times2
Embodiment 3
In the present embodiment, the system of the three-D nano-porous cuprous nano-chip arrays type negative electrode of lithium ion battery of copper/two dimensional oxidation Preparation Method is as follows:
By copper atom percentage is 80%, manganese atom percentage is 20% cupromanganese block wire cutting machine wire cutting at With a thickness of the cupromanganese piece of 0.6mm, successively with 380 mesh, 800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper to cupromanganese piece Surface is polished, and is then polished with the diamond polishing cream that granularity is 0.5 μm, the cupromanganese piece after polishing is placed in ultrasound In wave washer, it is cleaned by ultrasonic 5min under the conditions of 100W with dehydrated alcohol, takes out simultaneously naturally dry.
Using the cupromanganese piece Jing Guo above-mentioned processing as working electrode, using saturated calomel electrode as reference electrode, with Working electrode, reference electrode and auxiliary electrode are placed in corrosive liquid as auxiliary electrode, utilize electrochemical operation by platinum electrode The constant potential for applying 3.0V to working electrode and auxiliary electrode of standing carries out electrochemical corrosion, corrodes 90min, without gas in corrosive liquid Bubble generates, and completes cuprous nano array layers in the corrosion and three-D nano-porous copper base of cupromanganese piece at this time Load, formed negative electrode of lithium ion battery, gained negative electrode of lithium ion battery is taken out, with deionized water rinse 3 times, use ethyl alcohol again It rinses 3 times, is subsequently placed in vacuum oven, -0.1MPa in 75 DEG C of dry 10h and is cooled to room under the conditions of aforementioned vacuum Temperature;The corrosive liquid is the sulfuric acid solution that concentration is 50wt.%, and the dosage of corrosive liquid should at least flood working electrode completely.
Negative electrode of lithium ion battery production lithium ion battery manufactured in the present embodiment used below is simultaneously tested for the property.
It is to gather to electrode, using negative electrode of lithium ion battery manufactured in the present embodiment as working electrode, with micropore using metal lithium sheet Propylene is diaphragm, to contain 1M lithium hexafluoro phosphate (LiPF6) ethylene carbonate (EC), dimethyl carbonate (DMC) and carbonic acid two The mixed solution of ethyl ester (DEC) is electrolyte, and in the electrolyte, the volume ratio of EC, DMC and DEC are 1:1:1, full of argon gas, Water and oxygen content, which are below in the glove box of 1ppm, is assembled into lithium ion battery.Using the constant current of model NEWAREBTS-610 Charge and discharge instrument tests obtained lithium ion battery, and current density is 0.1mA/cm when test2, voltage range be 1.5~ 0.1V, test temperature are room temperature.Test result shows in charging and discharging currents density 0.1mA/cm2Under conditions of, the lithium-ion electric The first discharge specific capacity 3.1mAh/cm in pond2, capacity is maintained at 2.8mAh/cm after recycling 150 times2
Embodiment 4
In the present embodiment, the system of the three-D nano-porous cuprous nano-chip arrays type negative electrode of lithium ion battery of copper/two dimensional oxidation Preparation Method is as follows:
(1) the cupromanganese block that copper atom percentage is 35%, manganese atom percentage is 65% is cut with wire cutting machine line Be cut into the cupromanganese piece with a thickness of 0.5mm, successively with 380 mesh, 800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper to cupromanganese The surface of piece is polished, and is then polished with the diamond polishing cream that granularity is 0.5 μm, the cupromanganese piece after polishing is placed in In ultrasonic cleaner, it is cleaned by ultrasonic 4min under the conditions of 100W with dehydrated alcohol, takes out simultaneously naturally dry.
(2) electric using the cupromanganese piece by step (1) processing as working electrode, using saturated calomel electrode as reference Pole, using platinum electrode as auxiliary electrode, working electrode, reference electrode and auxiliary electrode are placed in corrosive liquid, electrochemistry is utilized The constant potential that work station applies 2.0V to working electrode and auxiliary electrode carries out electrochemical corrosion, corrodes 80min, in corrosive liquid Bubble-free generates, and completes cuprous nano piece battle array in the corrosion and three-D nano-porous copper base of cupromanganese piece at this time The load of column layer forms negative electrode of lithium ion battery, gained negative electrode of lithium ion battery is taken out, and rinses 6 times with deionized water, uses again Ethyl alcohol rinses 6 times, is subsequently placed in vacuum oven, -0.1MPa is cooled in 55 DEG C of dry 16h and under the conditions of aforementioned vacuum Room temperature;The corrosive liquid is the sulfuric acid solution that concentration is 35wt.%, and the dosage of corrosive liquid should at least flood working electrode completely.
Negative electrode of lithium ion battery production lithium ion battery manufactured in the present embodiment used below is simultaneously tested for the property.
It is to gather to electrode, using negative electrode of lithium ion battery manufactured in the present embodiment as working electrode, with micropore using metal lithium sheet Propylene is diaphragm, to contain 1M lithium hexafluoro phosphate (LiPF6) ethylene carbonate (EC), dimethyl carbonate (DMC) and carbonic acid two The mixed solution of ethyl ester (DEC) is electrolyte, and in the electrolyte, the volume ratio of EC, DMC and DEC are 1:1:1, full of argon gas, Water and oxygen content, which are below in the glove box of 1ppm, is assembled into lithium ion battery.Using the constant current of model NEWAREBTS-610 Charge and discharge instrument tests obtained lithium ion battery, and current density is 0.1mA/cm when test2, voltage range be 1.5~ 0.1V, test temperature are room temperature.Test result shows in charging and discharging currents density 0.1mA/cm2Under conditions of, the lithium-ion electric The first discharge specific capacity 2.9mAh/cm in pond2, capacity is maintained at 2.5mAh/cm after recycling 150 times2
Embodiment 5
In the present embodiment, the system of the three-D nano-porous cuprous nano-chip arrays type negative electrode of lithium ion battery of copper/two dimensional oxidation Preparation Method is as follows:
By copper atom percentage is 65%, manganese atom percentage is 35% cupromanganese block wire cutting machine wire cutting at With a thickness of the cupromanganese piece of 0.4mm, successively with 380 mesh, 800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper to cupromanganese piece Surface is polished, and is then polished with the diamond polishing cream that granularity is 0.5 μm, the cupromanganese piece after polishing is placed in ultrasound In wave washer, it is cleaned by ultrasonic 5min under the conditions of 100W with acetone, takes out simultaneously naturally dry.
Using the cupromanganese piece Jing Guo above-mentioned processing as working electrode, using saturated calomel electrode as reference electrode, with Working electrode, reference electrode and auxiliary electrode are placed in corrosive liquid as auxiliary electrode, utilize electrochemical operation by platinum electrode The constant potential for applying 1V to working electrode and auxiliary electrode of standing carries out electrochemical corrosion, corrodes 100min, without gas in corrosive liquid Bubble generates, and completes cuprous nano array layers in the corrosion and three-D nano-porous copper base of cupromanganese piece at this time Load, formed negative electrode of lithium ion battery, gained negative electrode of lithium ion battery is taken out, with deionized water rinse 5 times, use ethyl alcohol again It rinses 5 times, is subsequently placed in vacuum oven, -0.1MPa in 60 DEG C of dry 22h and is cooled to room under the conditions of aforementioned vacuum Temperature;The corrosive liquid is the sulfuric acid solution that concentration is 15wt.%, and the dosage of corrosive liquid should at least flood working electrode completely.
Negative electrode of lithium ion battery production lithium ion battery manufactured in the present embodiment used below is simultaneously tested for the property.
It is to gather to electrode, using negative electrode of lithium ion battery manufactured in the present embodiment as working electrode, with micropore using metal lithium sheet Propylene is diaphragm, to contain 1M lithium hexafluoro phosphate (LiPF6) ethylene carbonate (EC), dimethyl carbonate (DMC) and carbonic acid two The mixed solution of ethyl ester (DEC) is electrolyte, and in the electrolyte, the volume ratio of EC, DMC and DEC are 1:1:1, full of argon gas, Water and oxygen content, which are below in the glove box of 1ppm, is assembled into lithium ion battery.Using the constant current of model NEWAREBTS-610 Charge and discharge instrument tests obtained lithium ion battery, and current density is 0.1mA/cm when test2, voltage range be 1.5~ 0.1V, test temperature are room temperature.Test result shows in charging and discharging currents density 0.1mA/cm2Under conditions of, the lithium-ion electric The first discharge specific capacity 2.8mAh/cm in pond2, capacity is maintained at 2.4mAh/cm after recycling 150 times2

Claims (10)

1. a kind of cuprous nano-chip arrays type negative electrode of lithium ion battery of three-D nano-porous copper/two dimensional oxidation, it is characterised in that by Three-D nano-porous copper base and cuprous nano array layers composition, using three-D nano-porous copper base as collector, with Cuprous nano array layers are activity storage lithium layer, and cuprous nano array layers are located at the substrate surface and and substrate It is combined as a whole, cuprous nano array layers are made of the cuprous nano piece of growth in situ on the substrate.
2. the cuprous nano-chip arrays type negative electrode of lithium ion battery of three-D nano-porous copper/two dimensional oxidation according to claim 1, It is characterized in that in the cuprous nano array layers, cuprous nano piece perpendicular to three-D nano-porous copper base and Be staggered to form array structure, cuprous nano array layers with a thickness of 50nm~1.0 μm.
3. the cuprous nano-chip arrays type lithium ion battery of three-D nano-porous copper/two dimensional oxidation according to claim 1 or claim 2 is negative Pole, it is characterised in that the cuprous nano piece with a thickness of 2nm~60nm, the width of cuprous nano piece be 50nm~ 500nm, length are 100nm~1.5 μm.
4. the cuprous nano-chip arrays type lithium ion battery of three-D nano-porous copper/two dimensional oxidation according to claim 1 or claim 2 is negative Pole, it is characterised in that the pore-size of the three-D nano-porous copper base is 30nm~60nm, three-D nano-porous copper base With a thickness of 0.1mm~0.6mm.
5. the cuprous nano-chip arrays type negative electrode of lithium ion battery of three-D nano-porous copper/two dimensional oxidation according to claim 3, It is characterized in that the pore-size of the three-D nano-porous copper base is 30nm~60nm, the thickness of three-D nano-porous copper base Degree is 0.1mm~0.6mm.
6. the one of the three-D nano-porous cuprous nano-chip arrays type negative electrode of lithium ion battery of copper/two dimensional oxidation described in claim 1 One-step preparation method, it is characterised in that operation is as follows:
By cupromanganese piece sanding and polishing, then cleaned and dried with ethyl alcohol or acetone, using the cupromanganese piece after drying as Working electrode, using saturated calomel electrode as reference electrode, using platinum electrode as auxiliary electrode, by working electrode, reference electrode, It is placed in corrosive liquid with auxiliary electrode, it is rotten to carry out electrochemistry to the constant potential that working electrode and auxiliary electrode apply 0.1V~3.0V Erosion, corrosion form negative electrode of lithium ion battery when bubble-free generates into corrosive liquid, and negative electrode of lithium ion battery is taken out cleaning and is gone It in 45 DEG C~75 DEG C dryings and is cooled to room temperature except corrosive liquid, then under vacuum conditions;
The corrosive liquid is the sulfuric acid solution that concentration is 1wt.%~50wt.%, the oxygen concentration in corrosive liquid be 8mg/L~ The dosage of 10mg/L, corrosive liquid should at least flood working electrode completely.
7. the cuprous nano-chip arrays type negative electrode of lithium ion battery of three-D nano-porous copper/two dimensional oxidation according to claim 6 An one-step preparation method, it is characterised in that in the cupromanganese piece, the atomic percent of copper is 10%~80%, the atom hundred of manganese Divide than being 90%~20%.
8. the three-D nano-porous cuprous nano-chip arrays type lithium ion battery of copper/two dimensional oxidation described according to claim 6 or 7 is negative One one-step preparation method of pole, it is characterised in that the cupromanganese piece with a thickness of 0.1mm~0.6mm.
9. the three-D nano-porous cuprous nano-chip arrays type lithium ion battery of copper/two dimensional oxidation described according to claim 6 or 7 is negative One one-step preparation method of pole, it is characterised in that when corrosive liquid on cleaning removal negative electrode of lithium ion battery, successively with deionized water and Ethyl alcohol is cleaned.
10. the three-D nano-porous cuprous nano-chip arrays type lithium ion battery of copper/two dimensional oxidation described according to claim 6 or 7 One one-step preparation method of cathode, it is characterised in that be under vacuum conditions 10h~36h in 45 DEG C~75 DEG C dry times.
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CN107293754B (en) * 2017-07-26 2020-09-22 清华大学深圳国际研究生院 Preparation method of negative porous copper current collector for lithium metal battery
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CN108193255B (en) * 2018-01-30 2019-09-06 河北工业大学 A kind of supported porous cuprous nano piece composite material and preparation method of nano porous copper
CN108295854B (en) * 2018-01-30 2019-06-14 河北工业大学 A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material and preparation method
CN109301203B (en) * 2018-09-21 2020-01-10 四川大学 Copper/copper oxide/tin dioxide/carbon cathode of three-dimensional sea urchin/porous composite structure lithium ion battery and preparation method thereof
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