CN109524622A - One one-step preparation method of three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy - Google Patents
One one-step preparation method of three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy Download PDFInfo
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- H01M4/00—Electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The present invention provides one one-step preparing methods of three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy, by copper-tin alloy piece sanding and polishing, progress removal alloying processing in the mixed solution for being placed on hydrofluoric acid and nitric acid is washed with water, nano porous copper is formed during removal alloying and grows the cuprous nano film of covering nano porous copper in nano porous copper surface in situ, controlling removal alloying temperature is 50~90 DEG C, removal alloying processing is completed after the tin in copper-tin alloy completely removes, then water and ethanol washing are used, up to three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery.Method of the invention can simplify the production technology of negative electrode of lithium ion battery and effectively improve the cycle performance and high rate performance of negative electrode of lithium ion battery.
Description
Technical field
The invention belongs to negative electrode of lithium ion battery fields, are related to a kind of three-dimensional cuprous oxide-nanometer based on copper-tin alloy
One one-step preparation method of Porous Cu negative electrode of lithium ion battery.
Background technique
Lithium ion battery has open-circuit voltage high, and the service life is long, and energy density is high, memory-less effect and environmental-friendly etc. excellent
Point is widely used in portable mobile communication equipment, laptop and power storage device etc..Although traditional negative electrode material
Graphite, which has been obtained, to be widely applied, but because its lower specific capacity greatly limits lithium ion battery in electric car,
The application of field of hybrid electric vehicles.Improve the key of performance of lithium ion battery first is that find suitable negative electrode material, make lithium
Ion battery can satisfy ever-increasing energy storage demand.
Transition metal oxide (such as Fe, Co, Ni, Cu base oxide) is because of its higher theoretical specific capacity, environmental-friendly, valence
The reasons such as lattice are cheap, receive the extensive concern of researcher, show in terms of next-generation lithium ion battery negative material
Huge potentiality.However, lying across always in face of practical application transition metal oxide is as lithium ion battery negative material
Huge problem does not solve still.For example, the enormousness expansion generated in charge and discharge process, will lead to active material from collection
It falls off on fluid, capacity sharp-decay.Transition metal oxide is generally semiconductor, and conductivity is lower, this will cause charge and discharge
The reaction of electric process active material is insufficient, and charge/discharge capacity is reduced.
In order to solve the problems, such as that transition metal oxide exists, mainly take three kinds of methods at present: nanosizing, filming with
And surface coating.Nanosizing is the size by reducing negative electrode material, to reduce the volume expansion in charge and discharge process, simultaneously
The diffusion length for reducing lithium ion, increases the specific surface area of electrode material, to improve cyclical stability and capacity retention ratio.It is thin
Membranization is so that active material is attached to collection liquid surface using thin-film material mechanical strength with higher, improve following for material
Ring performance.Surface coating is to improve it by coating one layer of conductive materials (such as C, ppy) on transition metal oxide surface and lead
Electric rate, to improve its specific capacity and high rate performance.Although above-mentioned three kinds of methods can solve transition metal to a certain extent
Some problems existing for oxide, however have got long long way to go apart from actual application.
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 in the hole of nano porous copper
Cuprous oxide film is formed on wall surface, obtains negative electrode of lithium ion battery.This method needs first to prepare nano porous copper, then cooperates bonding
Agent and solvent modulation slurry are simultaneously coated in foamed nickel current collector, and dry and heated oxide is formed in the wall surface of the hole of nano porous copper
Cuprous oxide film, operating procedure is more, complex production process, is not conducive to the reduction of production costs and accomplishes scale production.Meanwhile
Nano porous copper carrier is first made in this method, and secondary treatment obtains oxidation Asia again after being bonded in porous nickel by binder
Copper, bonding and secondary treatment are easy to make the pollution of nano porous copper carrier surface and adsorbing contaminant atom, this can not only cause and oxygen
The binding force changed between cuprous is deteriorated, and can hinder electron-transport, and electrode polarization and impedance increase, and high rate performance is bad.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of, and the three-dimensional oxidation based on copper-tin alloy is sub-
One one-step preparation method of copper-nano porous copper negative electrode of lithium ion battery, with simplify negative electrode of lithium ion battery production technology and effectively
Improve the cycle performance and high rate performance of negative electrode of lithium ion battery.
Three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery one step provided by the invention based on copper-tin alloy
The preparation method operates as follows:
By copper-tin alloy piece sanding and polishing, it is washed with water in the mixed solution for being placed on hydrofluoric acid and nitric acid and carries out alloy
Change processing, during removal alloying formed nano porous copper and nano porous copper surface in situ grow covering nanometer it is more
The cuprous nano film of hole copper, control removal alloying temperature is 50~90 DEG C, after the tin in copper-tin alloy completely removes
Removal alloying processing is completed, it is then negative to get three-dimensional cuprous oxide-nano porous copper lithium ion battery with water and ethanol washing
Pole；
In the mixed solution of hydrofluoric acid and nitric acid, the concentration of hydrofluoric acid is 1wt.%~5wt.%, and concentration of nitric acid is
1wt.%~5wt.%, the atomic percent of copper and tin is (100-X): X in copper-tin alloy piece, wherein X is 24.5~65.
Above-mentioned one one-step preparation method of three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy
In technical solution, in copper-tin alloy piece, the atomic percent of copper and tin is (100-X): X, wherein X is preferably 35~50.
Above-mentioned one one-step preparation method of three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy
In technical solution, in the mixed solution of hydrofluoric acid and nitric acid, the concentration of hydrofluoric acid is preferably 3wt.%~5wt.%, concentration of nitric acid
Preferably 1wt.%~3wt.%.
Above-mentioned one one-step preparation method of three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy
In technical solution, preferably control removal alloying temperature is 80~90 DEG C.
Above-mentioned one one-step preparation method of three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy
In technical solution, the thickness of copper-tin alloy piece is preferably 250~450 μm, when the thickness of copper-tin alloy piece in the range when, it is excellent
The removal alloying time of choosing is 1~5h.
The above-mentioned one one-step preparation method system of three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy
Standby three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery, by nano porous copper and growth in situ in nano porous copper
The cuprous oxide film on surface forms, and the pore structure of the negative electrode of lithium ion battery is co-continuous, the isotypy pore structure of aperture, hole
Gap size is in 50~200nm range, and the thickness of cuprous oxide film is in 5nm or so, usually 4~10nm.
In technical solution of the present invention, cuprous oxide film is that dynamic growth comes out in copper-tin alloy corrosion process,
Under the synergistic effect of hydrofluoric acid and nitric acid, the lower tin of electrochemical potentials is gradually dissolved, in the mixing of hydrofluoric acid and nitric acid
Phase separation constantly occurs on solution and copper-tin alloy interface, meanwhile, copper is constantly spread, self assembly obtains nanoporous knot
Structure.During removal alloying, it is sub- to obtain oxidation in conjunction with the oxygen in solution for the nano porous copper of nitric acid oxidation surface high activity
Copper nano thin-film growth in situ on the surface of nano porous copper, cuprous oxide active material and nano porous copper it is carrier close-coupled at
Shape, growth in situ can effectively avoid the pollution of nano porous copper carrier surface and adsorbing contaminant atom, and therefore, cuprous nano is thin
Film and nano porous copper have very high binding force and extremely low interface resistance, this is conducive to improve cathode provided by the invention
Cycle performance and high rate performance.
Compared with prior art, present invention produces technical effects beneficial below:
1. the present invention provides an a kind of one-step preparation method of three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery,
Need to only handle in the solution by a step can prepare negative electrode of lithium ion battery, handle with the removal alloying that the prior art uses
It is compared in conjunction with the mode of thermal oxidation, the technological operation of the method for the invention is simpler, advantageously reduces lithium-ion electric
The production cost of pond cathode, it is easier to realize the large-scale production of lithium-ion negative pole.
2. the cuprous nano film using the negative electrode of lithium ion battery of the method for the invention preparation is growth in situ
On nano porous copper carrier surface, the two integrated molding goes growth of oxygen in situ in alloy process in copper-tin alloy
Cuprous nano thin-film, it is possible to prevente effectively from the pollution of nano porous copper carrier surface and adsorbing contaminant atom, therefore, growth in situ exists
The cuprous nano film and nano porous copper on nano porous copper surface have very high binding force and extremely low interface resistance,
This cathode prepared by the method for the invention has excellent cycle performance and high rate performance.
3. lithium ion battery is assembled into using the negative electrode of lithium ion battery of the method for the invention preparation, in charging and discharging currents
Capacity retention ratio is 100% after recycling 500 times or even 700 times under conditions of density 100mA/g, while coulombic efficiency is stablized
97%, even 99% or more, there is very excellent cycle performance, all there is extraordinary capacity to keep under different multiplying powers
Rate, while the battery cathode of method preparation of the invention also has good volumetric properties.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of copper-tin alloy ingot surface in embodiment 1.
Fig. 2 is the EDS spectrogram of copper-tin alloy ingot in embodiment 1.
Fig. 3 is the stereoscan photograph on negative electrode of lithium ion battery surface prepared by embodiment 1.
Fig. 4 is the stereoscan photograph in negative electrode of lithium ion battery section prepared by embodiment 1.
Fig. 5 is transmission electron microscope photo of the negative electrode of lithium ion battery of the preparation of embodiment 1 under different amplification.
Fig. 6 is the XRD spectra of negative electrode of lithium ion battery prepared by embodiment 1.
Fig. 7 is the constant current cycle performance curve of lithium ion battery prepared by embodiment 1.
Fig. 8 is the high rate performance curve of lithium ion battery prepared by embodiment 1.
Fig. 9 is the stereoscan photograph on negative electrode of lithium ion battery surface prepared by embodiment 2.
Figure 10 is the stereoscan photograph in negative electrode of lithium ion battery section prepared by embodiment 2.
Figure 11 is the stereoscan photograph on negative electrode of lithium ion battery surface prepared by embodiment 3.
Figure 12 is the stereoscan photograph in negative electrode of lithium ion battery section prepared by embodiment 3.
Figure 13 is the constant current cycle performance curve of lithium ion battery prepared by embodiment 4.
Specific embodiment
By the following examples three-dimensional cuprous oxide-nano porous copper lithium to provided by the invention based on copper-tin alloy from
One one-step preparation method of sub- battery cathode is described further.It is necessary to note that following embodiment is served only for making into one the present invention
Step explanation should not be understood as limiting the scope of the invention, and one of ordinary skill in the art are according to foregoing invention content to this
Invention is made some nonessential modifications and adaptations and is embodied, and the protection scope of invention is still fallen within.
Embodiment 1
In the present embodiment, three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy is provided
One one-step preparation method, the specific steps are as follows:
(1) copper billet and block tin are weighed according to the ratio that the atomic percent of copper and tin is 65:35, melting obtains in Muffle furnace
To copper-tin alloy ingot.The stereoscan photograph of copper-tin alloy ingot surface as shown in Figure 1, copper-tin alloy ingot EDS spectrogram such as Fig. 2 institute
Show.
(2) by copper-tin alloy ingot wire cutting machine cutting at the copper-tin alloy piece with a thickness of 400 μm, successively with 380 mesh,
800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper polish the surface of copper-tin alloy piece, be then 0.5 μm of Buddha's warrior attendant with granularity
The polishing of stone antiscuffing paste, the copper-tin alloy piece after polishing is cleaned with deionized water in the mixed solution for being placed on hydrofluoric acid and nitric acid
In the mixed solution of progress removal alloying processing, hydrofluoric acid and nitric acid, the concentration of hydrofluoric acid is 5wt.%, and concentration of nitric acid is
1wt.%, during removal alloying formed nano porous copper and nano porous copper surface in situ grow covering nanometer it is more
The cuprous oxide film of hole copper is 90 DEG C by the temperature that water-bath controls removal alloying, and it is 5h that the alloy treatment time is gone in control, so
Afterwards respectively with deionized water and ethanol washing 3 times to get three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery.
Fig. 3 and Fig. 4 is respectively the stereoscan photograph on negative electrode of lithium ion battery surface and section manufactured in the present embodiment, by
It is found that the pore structure of the negative electrode of lithium ion battery is co-continuous, the isotypy pore structure of aperture, average pore size is about for Fig. 3~4
200nm.Fig. 5 is the transmission electron microscope photo of negative electrode of lithium ion battery manufactured in the present embodiment, as shown in Figure 5, the lithium ion battery
In cathode, cuprous oxide film is evenly distributed on nano porous copper surface, shows the CuO in removal alloying processing2It is in situ uniform
Be grown on the matrix of nano porous copper, the thickness of cuprous oxide film is about 5nm.Fig. 6 is lithium ion prepared by embodiment 1
The XRD spectra of battery cathode, it will be appreciated from fig. 6 that negative electrode of lithium ion battery manufactured in the present embodiment is by pure Cu and CuO2Composition.
Lithium ion battery is made using negative electrode of lithium ion battery manufactured in the present embodiment below and is 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 100mA/g when test, and voltage range is 0.01~
3.0V, test temperature are room temperature.Test results are shown in figure 7, uses the negative electrode of lithium ion battery group of the present embodiment as shown in Figure 7
Capacity is not decayed after the lithium ion battery dressed up recycles 500 times under conditions of charging and discharging currents density 100mA/g, capacity
Conservation rate is 100%, while coulombic efficiency is stablized 99% or more, and there are also the trend constantly risen for specific capacity.In charge and discharge
Electric current is close be 100~5000mA/g in the range of recycle 130 times, testing example 1 prepare lithium ion battery it is forthright again
Can, as a result as shown in figure 8, as shown in Figure 8, the lithium ion battery being assembled into using the negative electrode of lithium ion battery of the present embodiment is not
There is extraordinary capacity retention ratio under same multiplying power.By Fig. 7~8 it can also be seen that negative electrode of lithium ion battery provided in this embodiment
Specific capacity with higher.This shows three-dimensional cuprous oxide-nano porous copper lithium ion battery using the method for the present invention preparation
The cyclical stability of cathode is excellent, can preferably solve the problems, such as that transition metal oxide exists.
Embodiment 2
In the present embodiment, three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy is provided
One one-step preparation method, the specific steps are as follows:
(1) copper billet and block tin are weighed according to the ratio that the atomic percent of copper and tin is 35:65, melting obtains in Muffle furnace
To copper-tin alloy ingot.
(2) by copper-tin alloy ingot wire cutting machine cutting at the copper-tin alloy piece with a thickness of 250 μm, successively with 380 mesh,
800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper polish the surface of copper-tin alloy piece, be then 0.5 μm of Buddha's warrior attendant with granularity
The polishing of stone antiscuffing paste, the copper-tin alloy piece after polishing is cleaned with deionized water in the mixed solution for being placed on hydrofluoric acid and nitric acid
In the mixed solution of progress removal alloying processing, hydrofluoric acid and nitric acid, the concentration of hydrofluoric acid is 5wt.%, and concentration of nitric acid is
5wt.%, during removal alloying formed nano porous copper and nano porous copper surface in situ grow covering nanometer it is more
The cuprous oxide film of hole copper is 60 DEG C by the temperature that water-bath controls removal alloying, and it is 3h that the alloy treatment time is gone in control, so
Afterwards respectively with deionized water and ethanol washing 3 times to get three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery.This reality
The stereoscan photograph difference on the negative electrode of lithium ion battery surface and section of applying example preparation is as shown in Figure 9 and Figure 10.
Embodiment 3
In the present embodiment, three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy is provided
One one-step preparation method, the specific steps are as follows:
(1) copper billet and block tin are weighed according to the ratio that the atomic percent of copper and tin is 75.5:24.5, is melted in Muffle furnace
Refining obtains copper-tin alloy ingot.
(2) by copper-tin alloy ingot wire cutting machine cutting at the copper-tin alloy piece with a thickness of 400 μm, successively with 380 mesh,
800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper polish the surface of copper-tin alloy piece, be then 0.5 μm of Buddha's warrior attendant with granularity
The polishing of stone antiscuffing paste, the copper-tin alloy piece after polishing is cleaned with deionized water in the mixed solution for being placed on hydrofluoric acid and nitric acid
In the mixed solution of progress removal alloying processing, hydrofluoric acid and nitric acid, the concentration of hydrofluoric acid is 5wt.%, and concentration of nitric acid is
1wt.%, during removal alloying formed nano porous copper and nano porous copper surface in situ grow covering nanometer it is more
The cuprous oxide film of hole copper is 90 DEG C by the temperature that water-bath controls removal alloying, and it is 5h that the alloy treatment time is gone in control, so
Afterwards respectively with deionized water and ethanol washing 3 times to get three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery.This reality
The stereoscan photograph difference on the negative electrode of lithium ion battery surface and section of applying example preparation is as is illustrated by figs. 11 and 12.
Embodiment 4
In the present embodiment, three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy is provided
One one-step preparation method, the specific steps are as follows:
(1) copper billet and block tin are weighed according to the ratio that the atomic percent of copper and tin is 60:40, melting obtains in Muffle furnace
To copper-tin alloy ingot.
(2) by copper-tin alloy ingot wire cutting machine cutting at the copper-tin alloy piece with a thickness of 450 μm, successively with 380 mesh,
800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper polish the surface of copper-tin alloy piece, be then 0.5 μm of Buddha's warrior attendant with granularity
The polishing of stone antiscuffing paste, the copper-tin alloy piece after polishing is cleaned with deionized water in the mixed solution for being placed on hydrofluoric acid and nitric acid
In the mixed solution of progress removal alloying processing, hydrofluoric acid and nitric acid, the concentration of hydrofluoric acid is 3wt.%, and concentration of nitric acid is
3wt.%, during removal alloying formed nano porous copper and nano porous copper surface in situ grow covering nanometer it is more
The cuprous oxide film of hole copper is 80 DEG C by the temperature that water-bath controls removal alloying, and it is 4h that the alloy treatment time is gone in control, this
When complete removal alloying processing, then respectively with deionized water and ethanol washing 3 times it is more to get three-dimensional cuprous oxide-nanometer
Hole copper negative electrode of lithium ion battery.
Embodiment 5
In the present embodiment, three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy is provided
One one-step preparation method, the specific steps are as follows:
(1) copper billet and block tin are weighed according to the ratio that the atomic percent of copper and tin is 50:50, melting obtains in Muffle furnace
To copper-tin alloy ingot.
(2) by copper-tin alloy ingot wire cutting machine cutting at the copper-tin alloy piece with a thickness of 350 μm, successively with 380 mesh,
800 mesh, 1200 mesh, 2000 mesh waterproof abrasive paper polish the surface of copper-tin alloy piece, be then 0.5 μm of Buddha's warrior attendant with granularity
The polishing of stone antiscuffing paste, the copper-tin alloy piece after polishing is cleaned with deionized water in the mixed solution for being placed on hydrofluoric acid and nitric acid
In the mixed solution of progress removal alloying processing, hydrofluoric acid and nitric acid, the concentration of hydrofluoric acid is 1wt.%, and concentration of nitric acid is
3wt.%, during removal alloying formed nano porous copper and nano porous copper surface in situ grow covering nanometer it is more
The cuprous oxide film of hole copper is 85 DEG C by the temperature that water-bath controls removal alloying, and it is 1h, hydrogen that the alloy treatment time is gone in control
Bubble-free generates in the mixed solution of fluoric acid and nitric acid, completes removal alloying processing at this time, then uses deionized water respectively
With ethanol washing 3 times to get three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery.
Lithium ion battery is made using negative electrode of lithium ion battery manufactured in the present embodiment below and is 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 100mA/g when test, and voltage range is 0.01~
3.0V, test temperature are room temperature.Test result is as shown in figure 13, uses the negative electrode of lithium ion battery of the present embodiment as shown in Figure 13
Capacity retention ratio is after the lithium ion battery being assembled into recycles 700 times under conditions of charging and discharging currents density 100mA/g
100%, coulombic efficiency is stablized 97% or more.Figure 13 also indicates that negative electrode of lithium ion battery provided in this embodiment is with higher
Specific capacity.
Claims (7)
1. one one-step preparation method of three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy, feature
It is:
By copper-tin alloy piece sanding and polishing, it is washed with water in the mixed solution for being placed on hydrofluoric acid and nitric acid and carries out at removal alloying
Reason forms nano porous copper during removal alloying and grows covering nano porous copper in nano porous copper surface in situ
Cuprous nano film, control removal alloying temperature be 50~90 DEG C, it is i.e. complete after the tin in copper-tin alloy completely removes
It is handled at removal alloying, then with water and ethanol washing to get three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery；
In the mixed solution of hydrofluoric acid and nitric acid, the concentration of hydrofluoric acid is 1wt.%~5wt.%, concentration of nitric acid be 1wt.%~
5wt.%, the atomic percent of copper and tin is (100-X): X in copper-tin alloy piece, wherein X is 24.5~65.
2. three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy according to claim 1
One one-step preparation method, which is characterized in that in copper-tin alloy piece, the atomic percent of copper and tin is (100-X): X, wherein X is 35~
50。
3. three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery according to claim 1 or claim 2 based on copper-tin alloy
An one-step preparation method, which is characterized in that in the mixed solution of hydrofluoric acid and nitric acid, the concentration of hydrofluoric acid be 3wt.%~
5wt.%, concentration of nitric acid are 1wt.%~3wt.%.
4. three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery according to claim 1 or claim 2 based on copper-tin alloy
An one-step preparation method, which is characterized in that control removal alloying temperature be 80~90 DEG C.
5. three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy according to claim 3
One one-step preparation method, which is characterized in that control removal alloying temperature is 80~90 DEG C.
6. three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery according to claim 1 or claim 2 based on copper-tin alloy
An one-step preparation method, which is characterized in that copper-tin alloy piece with a thickness of 250~450 μm.
7. three-dimensional cuprous oxide-nano porous copper negative electrode of lithium ion battery based on copper-tin alloy according to claim 6
One one-step preparation method, which is characterized in that the removal alloying time is 1~5h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110648852A (en) * | 2019-10-09 | 2020-01-03 | 温州大学 | Counter electrode and quantum dot sensitized solar cell |
| CN112349875A (en) * | 2020-10-23 | 2021-02-09 | 四川大学 | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method |
| CN113707890A (en) * | 2021-08-17 | 2021-11-26 | 复旦大学 | Au/Cu 2 O composite material, super-assembly preparation method and application |
| CN115863660A (en) * | 2022-12-09 | 2023-03-28 | 江苏正力新能电池技术有限公司 | Negative current collector of negative-electrode-free lithium battery and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104953104A (en) * | 2015-06-16 | 2015-09-30 | 华南理工大学 | Nano-porous and nano-porous flower shape copper-tin alloy and preparation method thereof |
| CN104986791A (en) * | 2015-06-19 | 2015-10-21 | 济南大学 | Preparation method for nanopore structure copper/cuprous oxide/copper oxide composite material |
| CN106207090A (en) * | 2016-07-29 | 2016-12-07 | 四川大学 | Three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type lithium ion battery negative and one one-step preparation method |
| CN106229462A (en) * | 2016-07-29 | 2016-12-14 | 四川大学 | Three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative and one one-step preparation method |
| CN108338161A (en) * | 2018-01-30 | 2018-07-31 | 河北工业大学 | A kind of supported porous silver oxide nanometer rod composite material of nano-porous silver and preparation method thereof |
-
2018
- 2018-11-13 CN CN201811345810.5A patent/CN109524622B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104953104A (en) * | 2015-06-16 | 2015-09-30 | 华南理工大学 | Nano-porous and nano-porous flower shape copper-tin alloy and preparation method thereof |
| CN104986791A (en) * | 2015-06-19 | 2015-10-21 | 济南大学 | Preparation method for nanopore structure copper/cuprous oxide/copper oxide composite material |
| CN106207090A (en) * | 2016-07-29 | 2016-12-07 | 四川大学 | Three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type lithium ion battery negative and one one-step preparation method |
| CN106229462A (en) * | 2016-07-29 | 2016-12-14 | 四川大学 | Three-D nano-porous copper/two dimensional oxidation cuprous nano-chip arrays type lithium ion battery negative and one one-step preparation method |
| CN108338161A (en) * | 2018-01-30 | 2018-07-31 | 河北工业大学 | A kind of supported porous silver oxide nanometer rod composite material of nano-porous silver and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| DEQUAN LIU等: "Preparation of 3D nanoporous copper-supported cuprous oxide for high-performance lithium ion battery", 《NANOSCALE》 * |
| WENBO LIU等: "A facile one-pot oxidation-assisted dealloying protocol to massively synthesize monolithic core-shell architectured nanoporous copper@ cuprous oxide nanonetworks for photodegradation of methyl orange", 《SCIENTIFIC REPORTS》 * |
| 禹贤斌 等: "去合金化制备纳米多孔铜及铜合金的最新研究进展", 《材料导报A:综述篇》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110648852A (en) * | 2019-10-09 | 2020-01-03 | 温州大学 | Counter electrode and quantum dot sensitized solar cell |
| CN112349875A (en) * | 2020-10-23 | 2021-02-09 | 四川大学 | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method |
| CN112349875B (en) * | 2020-10-23 | 2021-08-10 | 四川大学 | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method |
| CN113707890A (en) * | 2021-08-17 | 2021-11-26 | 复旦大学 | Au/Cu 2 O composite material, super-assembly preparation method and application |
| CN115863660A (en) * | 2022-12-09 | 2023-03-28 | 江苏正力新能电池技术有限公司 | Negative current collector of negative-electrode-free lithium battery and preparation method and application thereof |
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