CN109888167A - A kind of copper-based self-supporting CuO-Cu2The preparation method of O composite array sodium ion negative electrode material - Google Patents
A kind of copper-based self-supporting CuO-Cu2The preparation method of O composite array sodium ion negative electrode material Download PDFInfo
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- CN109888167A CN109888167A CN201910130572.4A CN201910130572A CN109888167A CN 109888167 A CN109888167 A CN 109888167A CN 201910130572 A CN201910130572 A CN 201910130572A CN 109888167 A CN109888167 A CN 109888167A
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Abstract
The present invention relates to a kind of CuO-Cu2The preparation method of O composite array material, belongs to secondary battery material field.Using foam copper as collector and copper source, it is calcined again after being performed etching by hydro-thermal method to copper surface, and then obtains the CuO-Cu of electrochemical performance2The composite array material of O.Specifically foam copper substrate is successively cleaned with deionized water, dehydrated alcohol and HCl before the reaction, defoam copper substrate surfaces greasy dirt and oxide layer；Ammonium persulfate and sodium hydroxide are successively dissolved in deionized water, are put into the foam copper substrate, then be transferred in water heating kettle, 6-8 h is reacted under steady temperature；Foam copper is taken out after reaction product natural cooling, vacuum drying is placed on after being washed with deionized, it is calcined at high temperature obtain final product later.The copper-based anode material of lithium-ion battery of high area capacitance amount and high circulation stability can be obtained by the above in-situ preparation method.
Description
Technical field
The present invention relates to a kind of CuO-Cu2The preparation method of O composite array material, belongs to sodium-ion battery field.With bubble
Foam copper again calcines it after being performed etching by hydro-thermal method to copper surface as collector and copper source, and then obtains electricity
The excellent CuO-Cu of chemical property2The composite array material of O.High area capacitance amount can be obtained by the above in-situ preparation method
With the copper-based anode material of lithium-ion battery of high circulation stability.
Background technique
With the increasingly depleted and excessive CO of the non-renewable energy resources such as coal, petroleum, natural gas2The effect of greenhouse caused by discharging
It should be on the rise, people, which begin one's study, makes full use of and store the method that green cleans solar energy.Lithium ion battery is from 20th century
Since the beginning of the nineties is commercialized for the first time by Sony, it has also become current important energy storage device is expected to become storage solar energy
Capital equipment.However the limited accretion of stock of the lithium on earth manufacturing cost of lithium ion battery, limit it further
Large-scale application.Sodium and lithium have similar chemical property, and rich reserves, are the important replacers of lithium ion battery, however
Poor energy density and cycle life limits the development of sodium-ion battery.Anode material of lithium-ion battery mainly includes carbon materials
Material, transition metal oxide, metal simple-substance etc..Finding suitable negative electrode material has important meaning for the development of sodium-ion battery
Justice.Transition metal oxide theoretical specific capacity with higher, but its biggish volume change meeting during embedding sodium/removing sodium
Cause electrode material to crush and hinder Ion transfer, biggish capacitance loss and cycle performance is caused to be decayed.CuO and Cu2The electricity of O
Material preparation in pole is mainly by coating method, but this method needs to add binder and conductive additive, hinders work
Property substance and electrolyte come into full contact with and increase ion internal resistance in the electrolytic solution, not only increase the cost of battery, and
Significantly reduce the energy density of battery.In recent years there are some self-supporting materials, be in simple terms exactly that itself can be used to do electricity
Pole, is not necessarily to other carriers, for example titanium sheet, carbon cloth and nickel foam etc., not only conducive to electronics quickly through also avoiding using adding
Add agent and conductive agent, and then improves the power density and energy density of battery.Single-phase CuO exists as anode material of lithium-ion battery
Serious volume deformation can be generated in charge and discharge process, cyclic reversibility is poor, and capacity attenuation is serious.And prepare compound CuO electricity
Pole material is believed to be effectively improved its chemical property.
Summary of the invention
For the electrochemical stability for improving CuO anode material of lithium-ion battery, technical solution of the present invention is proposed in foam
Copper-based bottom growth in situ CuO-Cu2The method of O composite material.The present invention using three-dimensional porous structure foam copper as substrate with
Copper source passes through hydro-thermal method and subsequent calcination process control CuO-Cu2The growth of O composite array material.
Specific preparation step are as follows: (1) foam copper substrate before the reaction successively with deionized water, dehydrated alcohol and HCl cleaned,
Defoam copper substrate surfaces greasy dirt and oxide layer.(2) ammonium persulfate and sodium hydroxide are successively dissolved in deionized water, are put
Enter foam copper and be transferred in water heating kettle and reacts at a constant temperature；(3) foam copper is taken out after natural cooling, is washed with deionized water
It is dried in vacuo after washing, it is calcined at high temperature obtain final product later.
Wherein, the molar ratio of ammonium persulfate and sodium hydroxide is 0.038-0.042:1.
Hydrothermal temperature is 120-150 DEG C in the step (2), the hydro-thermal reaction time 8-12h.Foam copper size
For the cm of 3 cm × 3, foam copper and water heating kettle bottom angle are 30 ~ 60o。
Calcining in the step (3) is to be sintered 1- after being warming up to 300-350 DEG C for 3-5 DEG C/min with heating rate
Obtained by 2h.Calcination process is in N2It is unfolded under gas shield.
In the present invention, CuO-Cu2O composite material is nano-sheet pattern, and the growth thickness on copper-based bottom is 2-5 μm,
Nanometer leaf length is 0.1-2 μm, with a thickness of 10-100 nm.It can be that sodium ion insertion and abjection mention for this nanometer chip architecture
For more active sites；The porous structure in three-dimensional porous foams copper can buffer CuO-Cu simultaneously2O composite material is recycling
Volume deformation in the process；CuO and Cu2The synergistic effect of O can also effectively improve battery performance.Foam copper prepared by the present invention
The CuO-Cu of load2O nanometer sheet electrode material may be directly applied to (lithium) sodium-ion battery cathode, not use binder and conduction
Agent.The features such as preparation method has preparation process simple, easy to operate.The CuO-Cu being prepared2O nanosheet composite material
Specific capacity with higher and stable cycle performance.
Detailed description of the invention
Fig. 1 is the SEM figure that embodiment 1 prepares electrode material.
Fig. 2 is the XRD spectrum that embodiment 1 prepares electrode material.
Fig. 3 is (a) cycle performance figure and (b) charge-discharge performance figure that embodiment 1 prepares electrode material.
Fig. 4 is the SEM figure that embodiment 2 prepares electrode material.
Fig. 5 is the XRD spectrum that embodiment 2 prepares electrode material.
Fig. 6 is (a) cycle performance figure and (b) charge-discharge performance figure that embodiment 2 prepares electrode material.
Fig. 7 is the SEM figure that embodiment 3 prepares electrode material.
Fig. 8 is the XRD spectrum that embodiment 3 prepares electrode material.
Fig. 9 is (a) cycle performance figure and (b) charge-discharge performance figure that embodiment 3 prepares electrode material.
Figure 10 is the SEM figure that embodiment 4 prepares electrode material.
Figure 11 is the XRD spectrum that embodiment 4 prepares electrode material.
Figure 12 is (a) cycle performance figure and (b) charge-discharge performance figure that embodiment 4 prepares electrode material.
Specific embodiment
Embodiment 1
0.6 ammonium persulfate and 2.5g sodium hydroxide are successively dissolved in 55mL deionized water, stir evenly and are transferred to 100mL
In reaction kettle.The foam copper cleaned (3 cm × 3cm) is placed in the water heating kettle and 120oIt is reacted under C steady temperature
8h.It is taken out after reacting end sample and being cooled to room temperature after successively being cleaned repeatedly with ethyl alcohol and deionized water 70oC vacuum drying
Array material can be obtained in dry 2 h in case.Fig. 1 is the SEM figure that embodiment 1 prepares array material, it can be seen that embodiment 1 is made
Standby obtained sample has apparent sheet-like array pattern, and single nanometer chip size is about 1 μm.Fig. 2 is prepared by embodiment 1
The XRD diagram of array material, it can be seen that its diffraction maximum is the peak of base foam copper, does not find the peak of CuO.But prepared material
Its chemical property is poor (Fig. 3) after expecting assembled battery.
Embodiment 2:
Foam copper loaded Cu2O electrode material: other conditions and embodiment 1 are identical, and obtained Cu base array material is placed in tubular type
It is calcined in furnace with nitrogen as protective gas, calcination temperature is 300 DEG C, and heating rate is 3 DEG C/min, and calcination time is
1h is then cooled to room temperature, and Cu can be obtained2O nano material.
Fig. 4 is the SEM figure that embodiment 2 prepares electrode material.From its SEM figure it can be seen that largely uniform with porose nanometer sheet
It is distributed in three-dimensional porous foams copper surface, these arrange compact nanometer sheet and form sheet-like array, constitute stable porous structure.
Fig. 5 is the XRD diagram that electrode material is prepared, in addition to foam copper substrate generate three strong peak other than, remaining diffraction maximum all with
Cu2The characteristic peak of O matches, it was demonstrated that final product Cu2O.It can be seen that its chemical property is (Fig. 6) similar to Example 1.
Embodiment 3:
Foam copper Supported CuO-Cu2O electrode material: 1.2g ammonium persulfate and 5.0g sodium hydroxide are successively dissolved in 50mL deionization
In water, stirs evenly and be transferred to 100mL reaction kettle；The rectangle foam copper foil (3 cm of size × 3cm) that one piece was cleaned
It is put into 100mL reaction kettle；It is put into after reaction kettle is tightened in baking oven and reacts 8h under 120 DEG C of steady temperatures.
Wait react but to room temperature, sample is taken out, successively with dry in 70 DEG C of vacuum after ethyl alcohol and deionized water repeatedly decontamination
Dry case dries dry 2 h, and CuO and Cu can be obtained2O composite nano materials.
Fig. 7 is the SEM figure that 3 system of embodiment prepares electrode material.It can be seen that we obtain on three-dimensional porous foams copper surface
Obtained more compact nanometer piece.Fig. 8 is the XRD diagram for preparing electrode material, other than the three strong peak that foam copper substrate generates,
Remaining diffraction maximum all with Cu2The characteristic peak of O and CuO matches, it was demonstrated that final product CuO-Cu2O composite nano materials.Fig. 9 is real
Apply the chemical property figure that example 3 prepares electrode material.It can see this CuO-Cu2O composite nano materials face with higher
Product specific capacity, in 0.8 mA cm-2Initial area specific capacity is up to 1.8 mAh cm under current density-2(Fig. 9 a), while its
It polarizes smaller (Fig. 9 b).
Embodiment 4:
Foam copper Supported CuO-Cu2O electrode material: other conditions and embodiment 3 are identical, and obtained Cu base array material is placed in
In N in tube furnace2It is calcined under gas shield, calcination temperature is 300 DEG C, and heating rate is 3 DEG C/min, and calcination time is
1h is then cooled to room temperature, and CuO and Cu can be obtained2O composite nano materials.
Figure 10 is the SEM figure that embodiment 4 prepares electrode material.It is uniform-distribution in three-dimensional porous foam copper substrate tight
Close connected nanometer sheet, nanometer chip architecture are very complete.
Figure 11 be embodiment 4 prepare electrode material XRD diagram, illustrate that array material that we are prepared is CuO-
Cu2O composite material.It is in 0.8 mA cm-2There is stable chemical property, area specific capacity can be stablized under current density
It is maintained at 1 mAh cm-2(Figure 12).
Claims (7)
1. a kind of copper-based self-supporting CuO-Cu2O composite array sodium ion cathode material preparation method, which is characterized in that including as follows
Step:
(1) foam copper substrate is successively cleaned with deionized water, dehydrated alcohol and HCl before the reaction, and defoam copper substrate surfaces
Greasy dirt and oxide layer；
(2) ammonium persulfate and sodium hydroxide are successively dissolved in deionized water, are put into foam copper substrate described in step (1), then
It is transferred in water heating kettle, 6-8 h is reacted under steady temperature；
(3) foam copper is taken out after the reaction product natural cooling of step (2), it is dry that vacuum is placed on after being washed with deionized
It is dry, it is calcined at high temperature obtain final product later.
2. copper-based self-supporting CuO-Cu according to claim 12O composite array sodium ion cathode material preparation method, it is special
Sign is that the molar ratio of ammonium persulfate and sodium hydroxide is 0.038-0.042:1.
3. copper-based self-supporting CuO-Cu according to claim 12O composite array sodium ion cathode material preparation method, it is special
Sign is that the HCl solution concentration is 1-3 M.
4. copper-based self-supporting CuO-Cu according to claim 12O composite array sodium ion cathode material preparation method, it is special
Sign is that hydrothermal temperature is 120-150 DEG C in step (2), the hydro-thermal reaction time 8-12h.
5. copper-based self-supporting CuO-Cu according to claim 12O composite array sodium ion cathode material preparation method, it is special
Sign is that the calcining in step (3) is with heating rate for 3-5 DEG C/min, is sintered obtained by 1-2h after being warming up to 300-350 DEG C,
Calcination process is in N2It is unfolded under gas shield.
6. copper-based self-supporting CuO-Cu according to claim 12O composite array sodium ion cathode material preparation method, it is special
Sign is, the copper-based self-supporting CuO-Cu2O composite array material is nano-sheet pattern, the growth on copper-based bottom
With a thickness of 2-5 μm, nanometer leaf length is 0.1-2 μm, with a thickness of 10-100 nm.
7. copper-based self-supporting CuO-Cu according to claim 12O composite array sodium ion cathode material preparation method, it is special
Sign is, the copper-based self-supporting CuO-Cu2O composite array material has porous structure, and pore-size distribution is 0.5-500 nm,
Specific surface area is 2-50 m2 g-1。
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Cited By (9)
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|---|---|---|---|---|
| CN110849813A (en) * | 2019-11-07 | 2020-02-28 | 曲阜师范大学 | CuO-Cu2Preparation method and application of O/CM nanowire array heterostructure |
| CN110849953A (en) * | 2019-11-22 | 2020-02-28 | 曲阜师范大学 | Loaded with Cu2O-CuO nanowire array composite material and preparation method thereof, biosensor and application thereof |
| 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 |
| CN113206253A (en) * | 2021-04-29 | 2021-08-03 | 陕西科技大学 | Foam copper potassium ion battery material and preparation method thereof |
| CN114351177A (en) * | 2022-01-14 | 2022-04-15 | 西北工业大学 | Preparation method of self-supporting electrode based on ultrasonic chemical surface reconstruction |
| CN114639819A (en) * | 2022-03-24 | 2022-06-17 | 中南大学 | Sodium-rich manganese-based oxide composite substrate metal oxide self-supporting binary anode material and preparation method thereof |
| CN114672847A (en) * | 2022-05-09 | 2022-06-28 | 中国科学技术大学 | Controllable preparation of high-performance electrocatalyst and application of high-performance electrocatalyst in preparation of urea by electrocatalysis coupling of carbon dioxide and nitrate radical |
| CN115010217A (en) * | 2022-04-18 | 2022-09-06 | 陕西科技大学 | Preparation method and application of three-dimensional composite electrode for efficiently removing nitrate in water through electro-catalysis |
| WO2024040889A1 (en) * | 2022-08-26 | 2024-02-29 | 五邑大学 | Cu-loaded nano-cuxo material, preparation method therefor, and application thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110849813A (en) * | 2019-11-07 | 2020-02-28 | 曲阜师范大学 | CuO-Cu2Preparation method and application of O/CM nanowire array heterostructure |
| CN110849953B (en) * | 2019-11-22 | 2022-10-25 | 曲阜师范大学 | Loaded Cu 2 Biosensor made of O-CuO nanowire array composite material and application of biosensor |
| CN110849953A (en) * | 2019-11-22 | 2020-02-28 | 曲阜师范大学 | Loaded with Cu2O-CuO nanowire array composite material and preparation method thereof, biosensor and application thereof |
| 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 |
| CN113206253A (en) * | 2021-04-29 | 2021-08-03 | 陕西科技大学 | Foam copper potassium ion battery material and preparation method thereof |
| CN114351177A (en) * | 2022-01-14 | 2022-04-15 | 西北工业大学 | Preparation method of self-supporting electrode based on ultrasonic chemical surface reconstruction |
| CN114351177B (en) * | 2022-01-14 | 2023-05-26 | 西北工业大学 | Preparation method of self-supporting electrode based on ultrasonic chemistry surface reconstruction |
| CN114639819A (en) * | 2022-03-24 | 2022-06-17 | 中南大学 | Sodium-rich manganese-based oxide composite substrate metal oxide self-supporting binary anode material and preparation method thereof |
| CN114639819B (en) * | 2022-03-24 | 2024-01-30 | 中南大学 | Sodium-rich manganese-based oxide composite substrate metal oxide self-supporting binary anode material and preparation method thereof |
| CN115010217A (en) * | 2022-04-18 | 2022-09-06 | 陕西科技大学 | Preparation method and application of three-dimensional composite electrode for efficiently removing nitrate in water through electro-catalysis |
| CN115010217B (en) * | 2022-04-18 | 2024-01-19 | 陕西科技大学 | Preparation method and application of three-dimensional composite electrode for efficiently removing nitrate in water by electrocatalytic reaction |
| CN114672847A (en) * | 2022-05-09 | 2022-06-28 | 中国科学技术大学 | Controllable preparation of high-performance electrocatalyst and application of high-performance electrocatalyst in preparation of urea by electrocatalysis coupling of carbon dioxide and nitrate radical |
| CN114672847B (en) * | 2022-05-09 | 2024-03-29 | 中国科学技术大学 | Controllable preparation of high-performance electrocatalyst and application of controllable preparation in preparation of urea by electrocatalytic coupling of carbon dioxide and nitrate |
| WO2024040889A1 (en) * | 2022-08-26 | 2024-02-29 | 五邑大学 | Cu-loaded nano-cuxo material, preparation method therefor, and application thereof |
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Application publication date: 20190614 |