CN106229462A - Three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative and one one-step preparation method - Google Patents
Three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative and one one-step preparation method Download PDFInfo
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- CN106229462A CN106229462A CN201610620678.9A CN201610620678A CN106229462A CN 106229462 A CN106229462 A CN 106229462A CN 201610620678 A CN201610620678 A CN 201610620678A CN 106229462 A CN106229462 A CN 106229462A
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a kind of three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative, this lithium ion battery negative is made up of three-D nano-porous copper base and cuprous nano array layers, with three-D nano-porous copper base as collector, lithium layer is stored up for activity with cuprous nano array layers, cuprous nano array layers is positioned at described substrate surface and is combined as a whole with substrate, cuprous nano array layers is made up of growth in situ cuprous nano sheet on the substrate, cuprous nano sheet is perpendicular to three-D nano-porous copper base and the formation array structure that is staggered, this lithium ion battery negative can improve cycle performance and the specific capacity of lithium ion battery.Present invention also offers an one-step preparation method of a kind of above-mentioned lithium ion battery negative, the method can effectively simplify the production technology of lithium ion battery negative.
Description
Technical field
The invention belongs to lithium ion battery negative field, particularly to a kind of lithium ion battery negative and preparation method thereof.
Background technology
At present, the negative material of commercial Li-ion battery is generally graphite, although graphite Stability Analysis of Structures, follows in discharge and recharge
Ring has stable reversible capacity, but weak point is its theoretical specific capacity only has 372mAh/g, it is difficult to meet the most quickly
Electronic equipment energy density higher to the lithium ion battery requirement of development, meanwhile, New Generation of Electric Vehicle and hybrid power vapour
The commercialized development of car, energy density and performance to lithium ion battery it is also proposed higher requirement, therefore have higher ratio
The novel negative pole of capacity is the study hotspot of current field of lithium.
Dequan Liu etc. discloses the nano porous copper with nickel foam as collector/Red copper oxide membranous type lithium ion battery
The preparation method (see Nanoscale, 2013,5,1917-1921.) of negative pole, the method is by Cu50Al50Alloy is placed in the hydrogen of 60 DEG C
In sodium hydroxide solution, nano porous copper is prepared in immersion, nano porous copper is made powdery and with polyvinylidene fluoride according to 9:1's
Mass ratio mixing in the case of adding a small amount of N-Methyl pyrrolidone forms slurry, and gained slurry is coated in nickel foam afflux
On body and under vacuum in 120 DEG C of dry 10h, the most in atmosphere in 140 DEG C of heating 3min i.e. at nano porous copper
Forming thickness on wall surface of the hole is 15～20nm Red copper oxide films, obtains lithium ion battery negative.The lithium of the method and preparation thereof from
Sub-battery cathode has the disadvantage that (1) the method needs first to prepare nano porous copper, then coordinates binding agent and solvent modulation
Slurry is also coated on nickel foam collector, drier also heated oxide forms Red copper oxide at the wall surface of the hole of nano porous copper
Film, operating procedure is many, complex production process；(2) owing to employing binding agent during preparing lithium ion battery negative, viscous
Knot agent itself is non-conductive and can not contribute capacity, electronics conduction can be caused to be obstructed and specific capacity reduces；(3) structure of this negative pole
Complexity, Red copper oxide film is positioned at the wall surface of the hole of nano porous copper, and nano porous copper is bonded in nickel foam surface, and electronics is transmitted to
The path of collector is longer, in addition the obstruction of binding agent, and this structure can seriously hinder electronics to conduct, and causes lithium ion battery
Cycle performance reduces；(4) Red copper oxide covers 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 so that Red copper oxide cannot be effectively improved as the electric conductivity of quasiconductor, and this is the most not
Being beneficial to electronics conduction, electronics conduction is obstructed and the cycle performance of lithium ion battery can be caused the best.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of three-D nano-porous copper/two dimensional oxidation is sub-
Copper nano-chip arrays type lithium ion battery negative and one one-step preparation method, to improve cycle performance and the specific volume of lithium ion battery
Amount, simplifies the production technology of lithium ion battery negative.
Three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative that the present invention provides, by
Three-D nano-porous copper base and cuprous nano array layers composition, with three-D nano-porous copper base as collector, with
Cuprous nano array layers is activity storage lithium layer, and cuprous nano array layers is positioned at described substrate surface and substrate
Being combined as a whole, cuprous nano array layers is made up of growth in situ cuprous nano sheet on the substrate.
In the cuprous nano array layers of above-mentioned lithium ion battery negative, cuprous nano sheet is perpendicular to three wieners
Rice Porous Cu substrate and the formation array structure that is staggered, the thickness of cuprous nano array layers is 50nm～1.0 μm.
In above-mentioned lithium ion battery negative, it is characterised in that the thickness of described cuprous nano sheet is 2nm～60nm, oxygen
The width changing cuprous nanometer sheet is 50nm～500nm, a length of 100nm～1.5 μm.The width of cuprous nano sheet and length
Represent the length of side and the length of side of longest edge of minor face in each cuprous nano sheet respectively.
In above-mentioned lithium ion battery negative, the pore-size of described three-D nano-porous copper base is 30nm～60nm, three
The thickness of dimension nano porous copper substrate is 0.1mm～0.6mm.
In above-mentioned lithium ion battery negative, cuprous nano sheet growth in situ refers on three-D nano-porous copper base
Cuprous nano sheet is grown directly upon described substrate surface.
The above-mentioned lithium ion battery negative that the present invention provides is in use, without adding any binding agent and conductive agent, directly
Connect the working electrode using this lithium ion battery negative as lithium ion battery, using metal lithium sheet or lithium source material as to electrode,
Suitable electrolyte and barrier film is used to be assembled into lithium-ion electric in the glove box that full argon and water content are up to standard with oxygen content
Pond.
Present invention also offers a kind of above-mentioned three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium-ion electric
One one-step preparation method of pond negative pole, operates as follows:
By cupromanganese sheet sanding and polishing, then clean with ethanol or acetone and be dried, with dried cupromanganese sheet
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 applying 0.1V～3.0V to working electrode and auxiliary electrode carries out electricity
Chemical attack, corrodes and forms lithium ion battery negative when producing to bubble-free in corrosive liquid, taken out by lithium ion battery negative
Clean and remove corrosive liquid, then be dried in 45 DEG C～75 DEG C and be cooled to room temperature under vacuum；
Described corrosive liquid be concentration be the sulfuric acid solution of 1wt.%～50wt.%, the oxygen concentration in corrosive liquid be 8mg/L～
10mg/L, the consumption of corrosive liquid should flood working electrode the most completely.
In said method, in described cupromanganese sheet, the atomic percent of copper is 10%～80%, the atomic percent of manganese
Being 90%～20%, cupromanganese sheet is formed by copper and the manganese casting of purity >=99.9wt.%.In order to reach to make lithium-ion electric
The requirement of strength of pond negative pole, the thickness of cupromanganese sheet is preferably 0.1mm～0.6mm, the concrete size of cupromanganese sheet according to
Practical application request is determined.
In said method, when cleaning the corrosive liquid removed on lithium ion battery negative, enter with deionized water and ethanol successively
Row cleans.
In said method, being dried in 45 DEG C～75 DEG C under vacuum is in order to avoid lithium ion battery time dry
Cuprous nano sheet in negative pole is oxidized, and preferred drying time is 10h～36h.
In said method, in order to form cuprous nano sheet on three-D nano-porous copper base surface, in corrosive liquid
Oxygen concentration is 8～10mg/L, due under normal pressure, room temperature condition, oxygen dissolubility of solution in aqueous phase solution be about 8～
10mg/L, i.e. can get, after therefore being diluted by concentrated sulphuric acid deionized water, the corrosive liquid that oxygen concentration is 8mg/L～10mg/L.
The principle of the method for the invention is as follows: in corrosive liquid, and in cupromanganese sheet, active higher manganese atom can be excellent
First corroded by selectivity, cause substantial amounts of copper atom to come out, due to not coordination around these copper atoms come out
Atom or coordination atom are little, and therefore these copper atoms have the mobility of height, can become metal cluster to diffusion aggregation around, with
Corrosion and the carrying out of copper atom reunion of manganese atom, the pit that cupromanganese sheet is formed can penetrate whole cupromanganese sheet also
Ultimately form three-D nano-porous copper base.And use electrochemical means, by applying constant potential, three-dimensional manometer not only can be made many
The formation speed of hole steel structure is accelerated, and can realize the controllability of nano-pore structure；Simultaneously as expose in corrosion process
Not having coordination atom or coordination atom little around the copper atom gone out, they can be combined by the oxygen in corrosive liquid, but this is the most not enough
To form Red copper oxide, the constant potential applied increases a driving force can to the combination of copper atom and oxygen, thus in three wieners
The surface of rice Porous Cu substrate is formed in cuprous nano array layers and this cuprous nano array layers, Red copper oxide
Nanometer sheet is perpendicular to three-D nano-porous copper base and the formation array structure that is staggered.
Compared with prior art, the method have the advantages that
1. the invention provides the lithium ion battery negative of a kind of new structure, this lithium ion battery negative is by three-dimensional manometer
Porous Cu substrate and cuprous nano array layers composition, three-D nano-porous copper base is received as collector and Red copper oxide
The carrier of rice array layers, cuprous nano chip arrays stores up lithium layer as activity, and three-D nano-porous copper is as collector not
Only there is excellent electric conductivity, and Red copper oxide change in volume in charge and discharge process can be alleviated to a certain extent, from
And improve the cycle performance of lithium ion battery, meanwhile, in cuprous nano array layers, cuprous nano sheet is perpendicular to three
Dimension nano porous copper substrate and the formation array structure that is staggered, this structure has high reference area, this can improve lithium from
The electrolyte of sub-battery and the contact area of Red copper oxide so that Red copper oxide is effectively changed as the electric conductivity of quasiconductor
Kind, high specific surface area can also shorten electronics conduction distance, improves electronics conduction velocity, beneficially cycle performance of lithium ion battery
Raising.
2. the lithium ion battery negative that the present invention provides without binding agent and is directly made with three-D nano-porous copper base
For collector, this not only can reduce the internal resistance of lithium ion battery largely, promote electronics conduction, improves 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, the lithium ion battery that the lithium ion battery negative provided with the present invention and lithium sheet are assembled into exists
0.1mA/cm2Electric current density under first discharge specific capacity be 2.4～3.2mAh/cm2, after circulating 150 times, capacity is maintained at
2.1～2.8mAh/cm2, there is higher first discharge specific capacity and good cycle charge discharge electrical property.
4. present invention also offers a kind of new method preparing lithium ion battery negative, the method is only by an one-step electrochemistry
Etching operation can form three-D nano-porous copper negative current collector and the load of cuprous nano array layers, nothing on it
Binding agent need to be used, compared with the manufacture method of existing lithium ion battery negative, the method simple to operate, not only effectively letter
Having changed the production technology of lithium ion battery negative, and can reduce the use of chemical reagent, beneficially lithium ion battery negative is raw
Produce reduction and the raising of production efficiency of cost.
Accompanying drawing explanation
Fig. 1 is the XRD curve of the lithium ion battery negative of embodiment 1 preparation；
Fig. 2 is the stereoscan photograph on the lithium ion battery negative surface of embodiment 1 preparation；
Fig. 3 is that the scanning electron microscope in the three-D nano-porous copper base cross section of the lithium ion battery negative of embodiment 1 preparation shines
Sheet；
Fig. 4 is the cycle performance curve of the lithium ion battery of embodiment 1 preparation.
Detailed description of the invention
By the following examples and combine accompanying drawing to the three-D nano-porous cuprous nanometer sheet of copper/two dimensional oxidation of the present invention
Array type lithium ion battery negative and one one-step preparation method are described further.
In following each embodiment, the compound method of corrosive liquid is as follows: under normal pressure, room temperature condition, by the dense sulfur of 98wt.%
Acid adds in deionized water, stirs and is configured to the sulfuric acid solution of respective concentration, i.e. can get oxygen concentration and be about 8～10mg/L
Corrosive liquid.
Embodiment 1
In the present embodiment, the system of three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative
Preparation Method is as follows:
Copper and manganese atom percentage ratio being the cupromanganese block wire cutting machine line of 50% and cuts into thickness is 0.4mm's
Cupromanganese sheet, polishes to the surface of cupromanganese sheet with 380 mesh, 800 mesh, 1200 mesh, the waterproof abrasive paper of 2000 mesh successively,
Then with the diamond polishing cream polishing that granularity is 0.5 μm, the cupromanganese sheet after polishing is placed in ultrasonic cleaner, uses
Dehydrated alcohol is ultrasonic cleaning 2min under the conditions of 100W, takes out and naturally dries.
Using through above-mentioned process cupromanganese sheet as working electrode, using saturated calomel electrode as reference electrode, with
Working electrode, reference electrode and auxiliary electrode, as auxiliary electrode, are placed in corrosive liquid, utilize electrochemical operation by platinum electrode
Stand and apply the constant potential of 0.4V to working electrode and auxiliary electrode and carry out electrochemical corrosion, corrode 60min, depletion of QI in corrosive liquid
Bubble produces, and the most i.e. completes cuprous nano array layers on the corrosion of cupromanganese sheet and three-D nano-porous copper base
Load, form lithium ion battery negative, gained lithium ion battery negative taken out, with deionized water rinsing 5 times, use ethanol again
Rinse 5 times, be subsequently placed in vacuum drying oven, in 65 DEG C of dry 20h and under the conditions of aforementioned vacuum, be cooled to room at-0.1MPa
Temperature；Described corrosive liquid be concentration be the sulfuric acid solution of 5wt.%, the consumption of corrosive liquid should flood working electrode the most completely.
The XRD curve of lithium ion battery negative prepared by 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 cross section of this lithium ion battery negative is as it is shown on figure 3, by Fig. 1
Understanding, this lithium ion battery negative is made up of copper and Red copper oxide, as shown in Figure 2, on the surface of three-D nano-porous copper base
Be loaded with cuprous nano array layers, from Fig. 2,3, in cuprous nano array layers, by cuprous nano
Sheet is perpendicular to three-D nano-porous copper base and the formation array structure that is staggered, and has high specific surface area, and Red copper oxide is received
The thickness of rice array layers is about 300nm, and wherein, the thickness of cuprous nano sheet is 10nm～30nm, cuprous nano
The width of sheet is 200nm～350nm, a length of 700nm～900nm, and the pore-size of three-D nano-porous copper base is for being about
40nm。
Lithium ion battery negative prepared by the present embodiment used below makes lithium ion battery and carries out performance test.
It is as working electrode, gather with micropore to electrode, the lithium ion battery negative prepared with the present embodiment with metal lithium sheet
Propylene is barrier film, with containing 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 this electrolyte, the volume ratio of EC, DMC and DEC is 1:1:1, full argon,
Water and oxygen content are below in the glove box of 1ppm being assembled into lithium ion battery.Using model is the constant current of NEWAREBTS-610
The lithium ion battery obtained is tested by discharge and recharge instrument, and during test, electric current density is 0.1mA/cm2, voltage range be 1.5～
0.1V, test temperature is room temperature.Test result shows, in charging and discharging currents density 0.1mA/cm2Under conditions of, this lithium-ion electric
First discharge specific capacity 3.2mAh/cm in pond2, after circulating 150 times, capacity is maintained at 2.6mAh/cm2, following of this lithium ion battery
Ring performance curve is as shown in Figure 4.
Embodiment 2
In the present embodiment, the system of three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative
Preparation Method is as follows:
By copper atom percentage ratio be 10%, manganese atom percentage ratio be 90% cupromanganese block wire cutting machine line cut into
Thickness is the cupromanganese sheet of 0.1mm, successively with 380 mesh, 800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper to cupromanganese sheet
Polishing in surface, then with the diamond polishing cream polishing that granularity is 0.5 μm, is placed in ultrasonic by the cupromanganese sheet after polishing
In ripple washer, with dehydrated alcohol ultrasonic cleaning 3min under the conditions of 100W, take out and naturally dry.
Using through above-mentioned process cupromanganese sheet as working electrode, using saturated calomel electrode as reference electrode, with
Working electrode, reference electrode and auxiliary electrode, as auxiliary electrode, are placed in corrosive liquid, utilize electrochemical operation by platinum electrode
Stand and apply the constant potential of 0.1V to working electrode and auxiliary electrode and carry out electrochemical corrosion, corrode 30min, depletion of QI in corrosive liquid
Bubble produces, and the most i.e. completes cuprous nano array layers on the corrosion of cupromanganese sheet and three-D nano-porous copper base
Load, form lithium ion battery negative, gained lithium ion battery negative taken out, with deionized water rinsing 4 times, use ethanol again
Rinsing 4 times, be subsequently placed in vacuum drying oven ,-0.1MPa is in 45 DEG C of dry 36h and is cooled to room under the conditions of aforementioned vacuum
Temperature；Described corrosive liquid be concentration be the sulfuric acid solution of 1wt.%, the consumption of corrosive liquid should flood working electrode the most completely.
Lithium ion battery negative prepared by the present embodiment used below makes lithium ion battery and carries out performance test.
It is as working electrode, gather with micropore to electrode, the lithium ion battery negative prepared with the present embodiment with metal lithium sheet
Propylene is barrier film, with containing 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 this electrolyte, the volume ratio of EC, DMC and DEC is 1:1:1, full argon,
Water and oxygen content are below in the glove box of 1ppm being assembled into lithium ion battery.Using model is the constant current of NEWAREBTS-610
The lithium ion battery obtained is tested by discharge and recharge instrument, and during test, electric current density is 0.1mA/cm2, voltage range be 1.5～
0.1V, test temperature is room temperature.Test result shows, in charging and discharging currents density 0.1mA/cm2Under conditions of, this lithium-ion electric
First discharge specific capacity 2.4mAh/cm in pond2, after circulating 150 times, capacity is maintained at 2.1mAh/cm2。
Embodiment 3
In the present embodiment, the system of three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative
Preparation Method is as follows:
By copper atom percentage ratio be 80%, manganese atom percentage ratio be 20% cupromanganese block wire cutting machine line cut into
Thickness is the cupromanganese sheet of 0.6mm, successively with 380 mesh, 800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper to cupromanganese sheet
Polishing in surface, then with the diamond polishing cream polishing that granularity is 0.5 μm, is placed in ultrasonic by the cupromanganese sheet after polishing
In ripple washer, with dehydrated alcohol ultrasonic cleaning 5min under the conditions of 100W, take out and naturally dry.
Using through above-mentioned process cupromanganese sheet as working electrode, using saturated calomel electrode as reference electrode, with
Working electrode, reference electrode and auxiliary electrode, as auxiliary electrode, are placed in corrosive liquid, utilize electrochemical operation by platinum electrode
Stand and apply the constant potential of 3.0V to working electrode and auxiliary electrode and carry out electrochemical corrosion, corrode 90min, depletion of QI in corrosive liquid
Bubble produces, and the most i.e. completes cuprous nano array layers on the corrosion of cupromanganese sheet and three-D nano-porous copper base
Load, form lithium ion battery negative, gained lithium ion battery negative taken out, with deionized water rinsing 3 times, use ethanol again
Rinsing 3 times, be subsequently placed in vacuum drying oven ,-0.1MPa is in 75 DEG C of dry 10h and is cooled to room under the conditions of aforementioned vacuum
Temperature；Described corrosive liquid be concentration be the sulfuric acid solution of 50wt.%, the consumption of corrosive liquid should flood working electrode the most completely.
Lithium ion battery negative prepared by the present embodiment used below makes lithium ion battery and carries out performance test.
It is as working electrode, gather with micropore to electrode, the lithium ion battery negative prepared with the present embodiment with metal lithium sheet
Propylene is barrier film, with containing 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 this electrolyte, the volume ratio of EC, DMC and DEC is 1:1:1, full argon,
Water and oxygen content are below in the glove box of 1ppm being assembled into lithium ion battery.Using model is the constant current of NEWAREBTS-610
The lithium ion battery obtained is tested by discharge and recharge instrument, and during test, electric current density is 0.1mA/cm2, voltage range be 1.5～
0.1V, test temperature is room temperature.Test result shows, in charging and discharging currents density 0.1mA/cm2Under conditions of, this lithium-ion electric
First discharge specific capacity 3.1mAh/cm in pond2, after circulating 150 times, capacity is maintained at 2.8mAh/cm2。
Embodiment 4
In the present embodiment, the system of three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative
Preparation Method is as follows:
(1) by copper atom percentage ratio be 35%, manganese atom percentage ratio be 65% cupromanganese block wire cutting machine line cut
Be slit into the cupromanganese sheet that thickness is 0.5mm, successively with 380 mesh, 800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper to cupromanganese
Polishing in the surface of sheet, then with the diamond polishing cream polishing that granularity is 0.5 μm, is placed in by the cupromanganese sheet after polishing
In ultrasonic cleaner, with dehydrated alcohol ultrasonic cleaning 4min under the conditions of 100W, take out and naturally dry.
(2) using the cupromanganese sheet that processes through step (1) as working electrode, using saturated calomel electrode as reference electricity
Pole, using platinum electrode as auxiliary electrode, working electrode, reference electrode and auxiliary electrode are placed in corrosive liquid, utilize electrochemistry
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 produces, and the most i.e. completes cuprous nano sheet battle array on the corrosion of cupromanganese sheet and three-D nano-porous copper base
The load of row layer, forms lithium ion battery negative, is taken out by gained lithium ion battery negative, with deionized water rinsing 6 times, uses again
Alcohol flushing 6 times, is subsequently placed in vacuum drying oven, and-0.1MPa in 55 DEG C of dry 16h and is cooled under the conditions of aforementioned vacuum
Room temperature；Described corrosive liquid be concentration be the sulfuric acid solution of 35wt.%, the consumption of corrosive liquid should flood working electrode the most completely.
Lithium ion battery negative prepared by the present embodiment used below makes lithium ion battery and carries out performance test.
It is as working electrode, gather with micropore to electrode, the lithium ion battery negative prepared with the present embodiment with metal lithium sheet
Propylene is barrier film, with containing 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 this electrolyte, the volume ratio of EC, DMC and DEC is 1:1:1, full argon,
Water and oxygen content are below in the glove box of 1ppm being assembled into lithium ion battery.Using model is the constant current of NEWAREBTS-610
The lithium ion battery obtained is tested by discharge and recharge instrument, and during test, electric current density is 0.1mA/cm2, voltage range be 1.5～
0.1V, test temperature is room temperature.Test result shows, in charging and discharging currents density 0.1mA/cm2Under conditions of, this lithium-ion electric
First discharge specific capacity 2.9mAh/cm in pond2, after circulating 150 times, capacity is maintained at 2.5mAh/cm2。
Embodiment 5
In the present embodiment, the system of three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative
Preparation Method is as follows:
By copper atom percentage ratio be 65%, manganese atom percentage ratio be 35% cupromanganese block wire cutting machine line cut into
Thickness is the cupromanganese sheet of 0.4mm, successively with 380 mesh, 800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper to cupromanganese sheet
Polishing in surface, then with the diamond polishing cream polishing that granularity is 0.5 μm, is placed in ultrasonic by the cupromanganese sheet after polishing
In ripple washer, with acetone ultrasonic cleaning 5min under the conditions of 100W, take out and naturally dry.
Using through above-mentioned process cupromanganese sheet as working electrode, using saturated calomel electrode as reference electrode, with
Working electrode, reference electrode and auxiliary electrode, as auxiliary electrode, are placed in corrosive liquid, utilize electrochemical operation by platinum electrode
Stand and apply the constant potential of 1V to working electrode and auxiliary electrode and carry out electrochemical corrosion, corrode 100min, depletion of QI in corrosive liquid
Bubble produces, and the most i.e. completes cuprous nano array layers on the corrosion of cupromanganese sheet and three-D nano-porous copper base
Load, form lithium ion battery negative, gained lithium ion battery negative taken out, with deionized water rinsing 5 times, use ethanol again
Rinsing 5 times, be subsequently placed in vacuum drying oven ,-0.1MPa is in 60 DEG C of dry 22h and is cooled to room under the conditions of aforementioned vacuum
Temperature；Described corrosive liquid be concentration be the sulfuric acid solution of 15wt.%, the consumption of corrosive liquid should flood working electrode the most completely.
Lithium ion battery negative prepared by the present embodiment used below makes lithium ion battery and carries out performance test.
It is as working electrode, gather with micropore to electrode, the lithium ion battery negative prepared with the present embodiment with metal lithium sheet
Propylene is barrier film, with containing 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 this electrolyte, the volume ratio of EC, DMC and DEC is 1:1:1, full argon,
Water and oxygen content are below in the glove box of 1ppm being assembled into lithium ion battery.Using model is the constant current of NEWAREBTS-610
The lithium ion battery obtained is tested by discharge and recharge instrument, and during test, electric current density is 0.1mA/cm2, voltage range be 1.5～
0.1V, test temperature is room temperature.Test result shows, in charging and discharging currents density 0.1mA/cm2Under conditions of, this lithium-ion electric
First discharge specific capacity 2.8mAh/cm in pond2, after circulating 150 times, capacity is maintained at 2.4mAh/cm2。
Claims (10)
1. three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative, it is characterised in that by
Three-D nano-porous copper base and cuprous nano array layers composition, with three-D nano-porous copper base as collector, with
Cuprous nano array layers is activity storage lithium layer, and cuprous nano array layers is positioned at described substrate surface and substrate
Being combined as a whole, cuprous nano array layers is made up of growth in situ cuprous nano sheet on the substrate.
The most three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative,
It is characterized in that in described cuprous nano array layers, cuprous nano sheet be perpendicular to three-D nano-porous copper base and
Be staggered formation array structure, and the thickness of cuprous nano array layers is 50nm～1.0 μm.
Three-D nano-porous copper/two dimensional oxidation the most according to claim 1 or claim 2 cuprous nano-chip arrays type lithium ion battery is born
Pole, it is characterised in that the thickness of described cuprous nano sheet is 2nm～60nm, the width of cuprous nano sheet be 50nm～
500nm, a length of 100nm～1.5 μm.
Three-D nano-porous copper/two dimensional oxidation the most according to claim 1 or claim 2 cuprous nano-chip arrays type lithium ion battery is born
Pole, it is characterised in that the pore-size of described three-D nano-porous copper base is 30nm～60nm, three-D nano-porous copper base
Thickness be 0.1mm～0.6mm.
The most three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative,
The pore-size that it is characterized in that described 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. an one-step preparation method of three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative,
It is characterized in that operation is as follows:
By cupromanganese sheet sanding and polishing, then clean with ethanol or acetone and be dried, using dried cupromanganese sheet as
Working electrode, using saturated calomel electrode as reference electrode, using platinum electrode as auxiliary electrode, by working electrode, reference electrode,
Being placed in corrosive liquid with auxiliary electrode, the constant potential applying 0.1V～3.0V to working electrode and auxiliary electrode carries out electrochemistry corruption
Erosion, corrodes and forms lithium ion battery negative when producing to bubble-free in corrosive liquid, lithium ion battery negative is taken out cleaning and goes
Except corrosive liquid, then it is dried in 45 DEG C～75 DEG C and is cooled to room temperature under vacuum；
Described corrosive liquid be concentration be the sulfuric acid solution of 1wt.%～50wt.%, the oxygen concentration in corrosive liquid be 8mg/L～
10mg/L, the consumption of corrosive liquid should flood working electrode the most completely.
The most three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative
An one-step preparation method, it is characterised in that in described cupromanganese sheet, the atomic percent of copper is 10%～80%, the atom hundred of manganese
Proportion by subtraction is 90%～20%.
8. bear according to three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery described in claim 6 or 7
One one-step preparation method of pole, it is characterised in that the thickness of described cupromanganese sheet is 0.1mm～0.6mm.
9. bear according to three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery described in claim 6 or 7
One one-step preparation method of pole, it is characterised in that when cleaning the corrosive liquid removed on lithium ion battery negative, successively with deionized water and
Ethanol is carried out.
10. according to three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery described in claim 6 or 7
One one-step preparation method of negative pole, it is characterised in that under vacuum in 45 DEG C～75 DEG C of dry times be 10h～36h.
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| CN107293754A (en) * | 2017-07-26 | 2017-10-24 | 清华大学深圳研究生院 | A kind of preparation method of the lithium metal battery porous copper current collector of negative pole |
| CN107732172A (en) * | 2017-09-25 | 2018-02-23 | 中国计量大学 | A kind of lithium ion battery negative material and preparation method thereof |
| CN108193255A (en) * | 2018-01-30 | 2018-06-22 | 河北工业大学 | A kind of supported porous cuprous nano piece composite material of nano porous copper and preparation method thereof |
| CN108295854A (en) * | 2018-01-30 | 2018-07-20 | 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 |
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