CN106207090B - Three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery and one one-step preparation method - Google Patents
Three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery and one one-step preparation method Download PDFInfo
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- CN106207090B CN106207090B CN201610616983.0A CN201610616983A CN106207090B CN 106207090 B CN106207090 B CN 106207090B CN 201610616983 A CN201610616983 A CN 201610616983A CN 106207090 B CN106207090 B CN 106207090B
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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
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- 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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- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery, the negative electrode of lithium ion battery is made of three-D nano-porous copper base and nano cuprous oxide wire layer, using the substrate as collector, it is activity storage lithium layer with nano cuprous oxide wire layer, nano cuprous oxide wire layer is located at the substrate surface and is combined as a whole with substrate, nano cuprous oxide wire layer is interweaved to stack by the nano cuprous oxide wire of growth in situ on the substrate and be formed, in network 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/one-dimensional oxidations
Copper nano-wire network-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.
Three-D nano-porous copper provided by the invention/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery, by
Three-D nano-porous copper base and nano cuprous oxide wire layer composition, using the substrate as collector, with nano cuprous oxide wire
Layer is activity storage lithium layer, and nano cuprous oxide wire layer is located at the substrate surface and is combined as a whole with substrate, and cuprous oxide is received
Rice noodles layer is made of the nano cuprous oxide wire of growth in situ on the substrate.
In the nano cuprous oxide wire layer of above-mentioned negative electrode of lithium ion battery, nano cuprous oxide wire is interweaved to stack and be formed
Network structure, nano cuprous oxide wire layer with a thickness of 10nm~300nm.
In above-mentioned negative electrode of lithium ion battery, the diameter of the nano cuprous oxide wire is 1nm~3nm, cuprous nano
The length of line is 30nm~500nm.
In above-mentioned negative electrode of lithium ion battery, the pore-size of the three-D nano-porous copper base is 20nm~50nm, three
Tie up nano porous copper substrate with a thickness of 0.1mm~0.6mm.
In above-mentioned negative electrode of lithium ion battery, nano cuprous oxide wire growth in situ refers on three-D nano-porous copper base
Nano cuprous oxide wire 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 copper/one-dimensional nano cuprous oxide wire network-type lithium-ion electrics
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, carry out electrification to working electrode and auxiliary electrode application -0.6V~0V constant potential
Corrosion is learned, corrosion forms negative electrode of lithium ion battery when bubble-free generates into corrosive liquid, negative electrode of lithium ion battery is taken out clear
It washes away except corrosive liquid, then in 45 DEG C~75 DEG C dryings and is 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
Nano cuprous oxide wire 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 nano cuprous oxide wire, 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 nano cuprous oxide wire layer and the nano cuprous oxide wire layer, nano cuprous oxide wire phase
Mutually interweave with stacking and forms network 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 nano cuprous oxide wire layer composition, nano cuprous oxide wire layer are located at substrate surface and are combined into one with substrate
Body, carrier of the three-D nano-porous copper base as collector and nano cuprous oxide wire layer, nano cuprous oxide wire layer conduct
Activity storage lithium layer, three-D nano-porous copper not only has excellent electric conductivity as collector, but also can delay to a certain extent
Volume change of the cuprous oxide in charge and discharge process is solved, so that the cycle performance of lithium ion battery is improved, meanwhile, by giving birth in situ
Growing nano cuprous oxide wire layer made of being interweaved and stack in the nano cuprous oxide wire on three-D nano-porous copper base is in
Reticular structure has high specific surface area, this can be improved the electrolyte of lithium ion battery and the contact area of cuprous oxide, makes
Cuprous oxide is obtained to be effectively improved as the electric conductivity of semiconductor, high specific surface area also can be shortened electronics conduction distance,
Electronics conduction of velocity is improved, the raising of cycle performance of lithium ion battery is conducive to.
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 2.3~3.0mAh/cm2, capacity is maintained at after recycling 150 times
2.0~2.6mAh/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 nano cuprous oxide wire layer thereon, without making
With binder, compared with the production method of existing negative electrode of lithium ion battery, this method it is easy to operate, be not only effectively simplified
The production technology of negative electrode of lithium ion battery, and can be reduced the use of chemical reagent, be conducive to negative electrode of lithium ion battery and be produced into
The raising of reduction originally and 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 partial sweep electromicroscopic photograph in negative electrode of lithium ion battery section prepared by embodiment 1；
Fig. 3 is the stereoscan photograph on negative electrode of lithium ion battery surface prepared by embodiment 1；
Fig. 4 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. 5 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 three-D nano-porous copper/nano cuprous oxide wire network of the present invention
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, three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery system
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 aforementioned 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
Stand and carry out electrochemical corrosion to the constant potential of working electrode and auxiliary electrode application -0.2V, corrode 60min, in corrosive liquid without
Bubble generates, and completes nano cuprous oxide wire layer in the corrosion and three-D nano-porous copper base of cupromanganese piece at this time
Load forms negative electrode of lithium ion battery, gained negative electrode of lithium ion battery is taken out, and rushes with deionized water flushing 5 times, again with ethyl alcohol
It washes 5 times, is subsequently placed in vacuum oven, in 65 DEG C of dry 20h and be 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 is as shown in Figure 1, the part in its section and surface sweep
It retouches electromicroscopic photograph and distinguishes as shown in Figures 2 and 3, the scanning electron microscope in the three-D nano-porous copper base section of the negative electrode of lithium ion battery
Photo is as shown in figure 4, as shown in Figure 1, which is made of copper and cuprous oxide, as shown in Figure 2, three-dimensional manometer
The area load of porous copper base has cuprous oxide nano wire layer, by Fig. 3,4 it is found that nano cuprous oxide wire layer is by giving birth in situ
The nano cuprous oxide wire grown on three-D nano-porous copper base is interweaved made of stacking, is in network structure, has height
Specific surface area, the thickness of nano cuprous oxide wire layer is about 65nm, wherein the diameter of nano cuprous oxide wire be 2nm~
The length of 3nm, nano cuprous oxide wire are 150nm~200nm, 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 NEWARE BTS-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 2.3mAh/cm after recycling 150 times2, which follows
Ring performance curve is as shown in Figure 5.
Embodiment 2
In the present embodiment, three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery system
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 aforementioned 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
Stand and carry out electrochemical corrosion to the constant potential of working electrode and auxiliary electrode application -0.6V, corrode 30min, in corrosive liquid without
Bubble generates, and completes nano cuprous oxide wire layer in the corrosion and three-D nano-porous copper base of cupromanganese piece at this time
Load forms negative electrode of lithium ion battery, gained negative electrode of lithium ion battery is taken out, and rushes with deionized water flushing 4 times, again with ethyl alcohol
It washes 4 times, is subsequently placed in vacuum oven, -0.1MPa is cooled to room temperature in 45 DEG C of dry 36h and under the conditions of aforementioned vacuum；
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 NEWARE BTS-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 2.3mAh/cm in pond2, capacity is maintained at 2.0mAh/cm after recycling 150 times2。
Embodiment 3
In the present embodiment, three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery system
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 aforementioned 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 0V to working electrode and auxiliary electrode of standing carries out electrochemical corrosion, corrodes 90min, bubble-free in corrosive liquid
It generates, is at this time the negative of nano cuprous oxide wire layer in the corrosion and three-D nano-porous copper base for complete cupromanganese piece
It carries, forms negative electrode of lithium ion battery, gained negative electrode of lithium ion battery is taken out, rinsed with deionized water flushing 3 times, again with ethyl alcohol
It 3 times, is subsequently placed in vacuum oven, -0.1MPa is cooled to room temperature in 75 DEG C of dry 10h and under the conditions of aforementioned vacuum；Institute
Stating 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 NEWARE BTS-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 3.0mAh/cm in pond2, capacity is maintained at 2.6mAh/cm after recycling 150 times2。
Embodiment 4
In the present embodiment, three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery system
Preparation Method is as follows:
By copper atom percentage is 35%, manganese atom percentage is 65% cupromanganese block wire cutting machine wire cutting at
With a thickness of the cupromanganese piece of 0.5mm, 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 4min under the conditions of 100W with dehydrated alcohol, takes out simultaneously naturally dry.
Using the cupromanganese piece Jing Guo aforementioned 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
Stand and carry out electrochemical corrosion to the constant potential of working electrode and auxiliary electrode application -0.4V, corrode 80min, in corrosive liquid without
Bubble generates, and completes nano cuprous oxide wire layer in the corrosion and three-D nano-porous copper base of cupromanganese piece at this time
Load forms negative electrode of lithium ion battery, gained negative electrode of lithium ion battery is taken out, and rushes with deionized water flushing 6 times, again with ethyl alcohol
It washes 6 times, is subsequently placed in vacuum oven, -0.1MPa is cooled to room temperature in 55 DEG C of dry 16h and under the conditions of aforementioned vacuum；
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 NEWARE BTS-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 2.0mAh/cm after recycling 150 times2。
Embodiment 5
In the present embodiment, three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery system
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 aforementioned 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
Stand and carry out electrochemical corrosion to the constant potential of working electrode and auxiliary electrode application -0.3V, corrode 100min, in corrosive liquid without
Bubble generates, and completes nano cuprous oxide wire layer in the corrosion and three-D nano-porous copper base of cupromanganese piece at this time
Load forms negative electrode of lithium ion battery, gained negative electrode of lithium ion battery is taken out, and rushes with deionized water flushing 5 times, again with ethyl alcohol
It washes 5 times, is subsequently placed in vacuum oven, -0.1MPa is cooled to room temperature in 60 DEG C of dry 22h and under the conditions of aforementioned vacuum；
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 NEWARE BTS-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 2.3mAh/cm after recycling 150 times2。
Claims (10)
1. a kind of three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery, it is characterised in that by
Three-D nano-porous copper base and nano cuprous oxide wire layer composition, using the substrate as collector, with nano cuprous oxide wire
Layer is activity storage lithium layer, and nano cuprous oxide wire layer is located at the substrate surface and is combined as a whole with substrate, and cuprous oxide is received
Rice noodles layer is made of the nano cuprous oxide wire of growth in situ on the substrate.
2. three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery according to claim 1,
It is characterized in that in the nano cuprous oxide wire layer, the nano cuprous oxide wire stacking that is interweaved forms network structure, aoxidizes
Cuprous nano wire layer with a thickness of 10nm~300nm.
3. three-D nano-porous copper according to claim 1 or claim 2/one-dimensional nano cuprous oxide wire network-type lithium ion battery is negative
Pole, it is characterised in that the diameter of the nano cuprous oxide wire is 1nm~3nm, the length of nano cuprous oxide wire be 30nm~
500nm。
4. three-D nano-porous copper according to claim 1 or claim 2/one-dimensional nano cuprous oxide wire network-type lithium ion battery is negative
Pole, it is characterised in that the pore-size of the three-D nano-porous copper base is 20nm~50nm, three-D nano-porous copper base
With a thickness of 0.1mm~0.6mm.
5. three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery according to claim 3,
It is characterized in that the pore-size of the three-D nano-porous copper base is 20nm~50nm, the thickness of three-D nano-porous copper base
Degree is 0.1mm~0.6mm.
6. three-D nano-porous copper described in claim 1/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery one
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 working electrode and auxiliary electrode application -0.6V~0V constant potential
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. three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery 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. three-D nano-porous copper described according to claim 6 or 7/one-dimensional nano cuprous oxide wire network-type lithium ion battery 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. three-D nano-porous copper described according to claim 6 or 7/one-dimensional nano cuprous oxide wire network-type lithium ion battery 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. three-D nano-porous copper described according to claim 6 or 7/one-dimensional nano cuprous oxide wire network-type lithium ion battery
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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| 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 |
| 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 |
| CN109811364B (en) * | 2019-01-10 | 2020-10-27 | 北京化工大学 | Ruthenium/cuprous oxide electro-catalytic material and preparation method thereof |
| CN111293324B (en) * | 2020-03-24 | 2021-06-08 | 成都新柯力化工科技有限公司 | Anti-oxidation gas diffusion layer of fuel cell and preparation method thereof |
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