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 PDFInfo
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention 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
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 |
| CN107732172B (en) * | 2017-09-25 | 2020-10-30 | 中国计量大学 | Lithium ion battery cathode material and preparation method thereof |
| 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 |
| 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 |
| 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 |
| CN110970596B (en) | 2018-09-29 | 2021-10-12 | 清华大学 | Lithium ion battery cathode, preparation method thereof and lithium ion battery |
| CN110963523B (en) * | 2018-09-29 | 2021-11-05 | 清华大学 | Nano porous copper loaded copper oxide nanosheet array composite material and preparation method thereof |
| CN109524622B (en) * | 2018-11-13 | 2020-02-11 | 四川大学 | One-step preparation method of three-dimensional cuprous oxide-nano porous copper lithium ion battery cathode based on copper-tin alloy |
| 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 |
| CN112921369B (en) * | 2021-01-28 | 2022-07-22 | 上海交通大学 | Lithium metal negative current collector surface thermal oxidation regulation and control method for prolonging cycle life |
Citations (2)
| 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 |
| CN102965711A (en) * | 2012-11-06 | 2013-03-13 | 上海交通大学 | Anodization two-step preparation method of cuprous oxide nanosheet powder material |
-
2016
- 2016-07-29 CN CN201610620678.9A patent/CN106229462B/en active Active
Patent Citations (2)
| 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 |
| CN102965711A (en) * | 2012-11-06 | 2013-03-13 | 上海交通大学 | Anodization two-step preparation method of cuprous oxide nanosheet powder material |
Non-Patent Citations (1)
| Title |
|---|
| Preparation of 3D nanoporous copper-supported cuprous oxide for high-performance lithium ion battery anodes;Dequan Liu等;《Nanoscale》;20130104;第5卷;第1917-1921页 |
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