CN107093703A - A kind of preparation method of manganese dioxide/foam copper sodium-ion battery self-supporting negative pole - Google Patents
A kind of preparation method of manganese dioxide/foam copper sodium-ion battery self-supporting negative pole Download PDFInfo
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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 invention discloses a kind of preparation method of manganese dioxide/foam copper sodium-ion battery self-supporting negative pole, clean dry obtains electrode matrix after sheet-formed foam copper is handled with absolute ethyl alcohol；Then certain density manganese sulfate solution is configured；Resulting solution and foam copper sheet are put into hydrothermal reaction kettle again, using hydro-thermal induction heating equipment heating and thermal insulation certain time, manganese dioxide/foam copper sodium-ion battery self-supporting negative pole with three-dimensional porous connection rack-like structure is produced.
Description
Technical field
The invention belongs to sodium-ion battery negative pole preparation field, and in particular to a kind of manganese dioxide/foam copper sodium ion electricity
The preparation method of pond self-supporting negative pole.
Background technology
Early in the 1980s, sodium-ion battery and lithium ion battery are studied simultaneously, with lithium ion battery into
Work(is commercialized, and the research of sodium-ion battery is gradually slowed down.Sodium and lithium belong to same main group, with similar physicochemical property, battery
Charge-discharge principle is basically identical.During charging, Na+Deviate from from positive electrode, negative material is embedded in by electrolyte, while electronics
Negative pole is transferred to by external circuit, charge balance is kept；It is then opposite during electric discharge.Compared with lithium ion battery, lithium ion battery tool
There are following characteristics：Sodium resource is cheap, nontoxic and rich reserves, widely distributed.In recent years, lithium ion battery is used as efficient energy storage
Device is widely used in portable electronic market, and expands to industries such as electric automobile, intelligent grid and large-scale power systems
Exhibition.From the point of view of the application demand of extensive energy storage, preferable secondary cell is in addition to suitable chemical property, it is necessary to simultaneous
Turn round and look at the economic results in society indexs such as aboundresources, price be cheap.More rare lithium resource can not effectively meet market
Great demand, the related energy storage technology for developing other cheap alternative lithium ion batteries is very crucial, therefore sodium-ion battery is again
It is secondary to obtain people's close attention.
The research that electrode material is sodium-ion battery technology is can be seen that according to the charge-discharge principle of sodium-ion battery to close
Key, only develops the positive and negative pole material suitable for the stable deintercalation of sodium ion, could promote the practical of sodium-ion battery.Metal oxygen
Due to it by electrochemically converting reaction and sodium ion the conversion of polyelectron reversible construction can occur for compound, therefore with high specific volume
Amount, and it is cheap, environment-friendly, therefore be the high power capacity sodium ion electricity of the great application prospect of a class as the new focus of research
Pond negative pole, wherein manganese dioxide due in nature rich content, cheap, high theoretical specific capacity (700-
1380F·g-1), and it is environmentally friendly, it is considered to be most promising electrode material.But the electric conductivity of manganese dioxide is poor and sends out
Raw Faraday pseudo-capacitance reaction is surface reaction, i.e., only could occur fake capacitance reaction at one layer of surface or very thin surface, this
So that the actual specific capacity of manganese dioxide only has 120-250Fg-1.Manganese dioxide is compounded in big specific surface area
On foam copper, using its bigger serface and excellent electric conductivity, disperse manganese dioxide, improve its electric capacity utilization rate.Mesh
The preceding common method for preparing electrode material manganese dioxide has hydro-thermal method, sol-gel process, sedimentation, microemulsion synthesis method.But
There is course of reaction and be difficult to control, have the low shortcoming of side reaction generation, product purity in precipitation method synthesis manganese dioxide, hydro-thermal method is closed
There is the shortcomings of reaction temperature is of a relatively high, the reaction time is longer into manganese dioxide.
The content of the invention
It is an object of the invention to provide a kind of preparation side of manganese dioxide/foam copper sodium-ion battery self-supporting negative pole
Method, to overcome the defect that above-mentioned prior art is present, the inventive method can be prepared a kind of with three-dimensional porous connection nanometer
Structure, larger specific surface area and the small sodium-ion battery self-supporting negative pole of itself internal resistance.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of preparation method of manganese dioxide/foam copper sodium-ion battery self-supporting negative pole, comprises the following steps：
1) self-supporting matrix sheet foam copper is cut to the foam copper sheet A of rectangle；
2) foam copper sheet A is immersed in after being cleaned by ultrasonic in acetone and obtains B with deionized water rinsing again；
3) B is immersed in absolute ethyl alcohol, and handled in ultrasound environments, then dry C；
4) manganese sulfate is dissolved in deionized water, MnSO is made in stirring4Solution D；
5) by MnSO4Solution D is transferred in hydro-thermal sensing kettle, is put into C, wherein 0.15~0.45g C are added in per 60mLD,
After kettle is sealed, it is placed in hydro-thermal induction heating equipment, with 400~600KHz induction frequencies by room temperature to 80~160
DEG C, and 1~3h is incubated, obtain manganese dioxide/foam carbon/carbon-copper composite material E；
6) manganese dioxide/foam carbon/carbon-copper composite material E is washed with deionized water and absolute ethyl alcohol respectively, be then dried to obtain
Manganese dioxide with three-dimensional porous rack-like connectivity structure/foam copper sodium-ion battery self-supporting negative pole.
Further, step 1) in sheet-formed foam copper thickness be 1mm, foam copper sheet A a length of 4cm, a width of 2.5cm.
Further, step 2) in acetone, step 3) in absolute ethyl alcohol and step 6) in absolute ethyl alcohol be analysis it is pure.
Further, step 2) the middle frequency that is cleaned by ultrasonic is 50KHz, and the ultrasonic cleaning time is 10~30min.
Further, step 3) in ultrasonically treated frequency be 50K Hz, sonication treatment time be 10~30min.
Further, step 3) in drying temperature be 60~80 DEG C, the time be 30~50min.
Further, step 4) in manganese sulfate is dissolved in deionized water, 0.005~0.01mol/L is made in stirring
MnSO4Solution D, is stirred using magnetic stirring apparatus, and speed is 600~800 revs/min, and the time is 10~30min.
Further, step 5) in C induction coils in hydro-thermal induction heating equipment magnetic induction line place.
Further, step 6) in F is washed using deionized water and absolute ethyl alcohol at room temperature, in drying process
Drying temperature is 80~160 DEG C, and the time is 6~10h.
Compared with prior art, the present invention has following beneficial technique effect：
The self-supporting two-dimensional nanostructure electrode that the present invention is constructed using hydro-thermal induction heating technique original position, using foam copper as
Supporter, while electric conductivity is improved, forms three-dimensional porous skeleton structure, plays a part of collector and conducting matrix grain, its
Surface in situ grown two-dimensional nano manganese dioxide thin slice；The thin slice of nanosizing shortens Na+Diffusion path, foam copper also has
Certain free space bears the expansion of electrode, improves the high rate performance and cycle performance of battery；Porous increases electricity
Pole and the contact area of electrolyte, so as to increase embedding lithium space, improve specific capacity；Porous connection can reduce ohmic internal resistance, profit
In electric transmission, charge transfer resistance is reduced.On the other hand, the side of self-supporting electrode is prepared using hydro-thermal induction heating technique
Method, eliminates the step of traditional electrode prepares film, and does not need binding agent and conductive agent, does not interfere with the capacity of electrode, contracts
Cost has been saved while short process flow.
In addition, the present invention is only propped up by the way of heating during hydro-thermal induction heating technique is different from tradition reaction and heat transfer
Support body foam copper is sensed, and is heated rapidly, and produces high activity reaction environment, accurate distribution nucleation site, and manganese dioxide is easy
With foam copper formation chemical bond, state of optimizing integration gives full play to both cooperative effects, while using hydro-thermal sensing heating skill
Art, crystal growth of the manganese dioxide on foam copper is controllable precise, by the size, frequency and stirring that change alternating current
Speed, can be achieved the control to reaction temperature, can suppress to reunite, nanosizing degree is high, is evenly distributed, therefore in sodium-ion battery
Show higher capacity, stable cycle performance and excellent high rate performance.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of sodium-ion battery self-supporting negative pole prepared by the embodiment of the present invention 1；
Fig. 2 is ESEM (SEM) photo of sodium-ion battery self-supporting negative pole prepared by the embodiment of the present invention 1；
Fig. 3 is the high rate performance figure of sodium-ion battery self-supporting negative pole prepared by the embodiment of the present invention 1,3,5.
Embodiment
Embodiments of the present invention are described in further detail below：
A kind of preparation method of manganese dioxide/foam copper sodium-ion battery self-supporting negative pole, comprises the following steps：
1) by thickness for 1mm self-supporting matrix sheet foam copper cut rectangle foam copper sheet A, make its a length of 4cm,
A width of 2.5cm；
2) 0.15~0.45g (i.e. 1~3) A is immersed in analytically pure acetone and cleans 10 with 50KHz frequency ultrasound
~30min, then takes out A, then with deionized water rinsing 3 times B；
3) 0.15~0.45g (i.e. 1~3) B is immersed in analytically pure absolute ethyl alcohol, and is 50KHz's in frequency
10~30min is handled in ultrasound environments, B is then taken out and is put into baking oven, 30~50min is dried in 60~80 DEG C of temperature and obtains C；
4) manganese sulfate is dissolved in deionized water, 10 is stirred with 600~800 revs/min of speed using magnetic stirring apparatus
The MnSO that molar concentration is 0.005~0.01mol/L is made in~30min4Solution D；
5) by 60ml MnSO4Solution D be transferred to hydro-thermal sensing kettle in, then by 0.15~0.45g (i.e. 1~3) C perpendicular to
The magnetic induction line direction of induction coil is put into hydro-thermal induction heating equipment, after kettle is sealed, and is placed in hydro-thermal induction heating equipment,
With 400~600KHz induction frequencies by room temperature to 80~160 DEG C, and 1~3h is incubated, obtains manganese dioxide/foam copper multiple
Condensation material E；
6) by E respectively with the deionized water and the soft washing of analytically pure absolute ethyl alcohol that temperature is room temperature, then 80~
6~10h is dried in 160 DEG C of temperature, the manganese dioxide with three-dimensional porous skeleton structure/foam copper sodium-ion battery is obtained certainly
Support negative pole.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
(1) by thickness for 1mm self-supporting matrix sheet foam copper cut rectangle foam copper sheet A, make its a length of
4cm, a width of 2.5cm；
(2) 0.15g A are immersed in analytically pure acetone and 20min are cleaned with 50KHz frequency ultrasound, then take out A,
Again with deionized water rinsing 3 times B；
(3) 0.15g B are immersed in analytically pure absolute ethyl alcohol, and handled in frequency is 50KHz ultrasound environments
20min, then takes out B and is put into baking oven, and 40min is dried in 70 DEG C of temperature and obtains C；
(4) manganese sulfate is dissolved in deionized water, 20min systems is stirred with 700 revs/min of speed using magnetic stirring apparatus
Obtain the MnSO that molar concentration is 0.008mol/L4Solution D；
(5) by 60mL MnSO4Solution D is transferred in hydro-thermal sensing kettle, then 0.15g C is set perpendicular to hydro-thermal sensing heating
The magnetic induction line direction of standby middle induction coil is put into, and after kettle is sealed, is placed in hydro-thermal induction heating equipment, with 500KHz sensing
Frequency, to 120 DEG C, and is incubated 2h by room temperature, obtains manganese dioxide/foam carbon/carbon-copper composite material E；
(6) by E respectively with the deionized water and the soft washing of analytically pure absolute ethyl alcohol that temperature is room temperature, then 120
DEG C temperature in dry 8h obtain the manganese dioxide with three-dimensional porous rack-like connectivity structure/foam copper sodium-ion battery self-supporting
Negative pole.
It will be seen from figure 1 that self-supporting negative pole good crystallinity prepared by embodiment 1, purity is higher；Figure it is seen that
Manganese dioxide/foam copper self-supporting the negative pole prepared in step (6) is three-dimensional porous rack-like connectivity structure and surface has sheet
The manganese dioxide of structure；From figure 3, it can be seen that manganese dioxide/foam copper self-supporting negative pole prepared by the present embodiment 1 is in sodium ion
Higher capacity, excellent multiplying power and cycle performance are shown in battery.
Embodiment 2
(1) by thickness for 1mm material self-supporting matrix sheet foam copper cut rectangle foam copper sheet A, grow it
For 4cm, a width of 2.5cm；
(2) 0.30g A are immersed in analytically pure acetone and 20min are cleaned with 50KHz frequency ultrasound, then take out A,
Again with deionized water rinsing 3 times B；
(3) 0.30g B are immersed in analytically pure absolute ethyl alcohol, and handled in frequency is 50KHz ultrasound environments
10min, then takes out B and is put into baking oven, and 30min is dried in 60 DEG C of temperature and obtains C；
(4) manganese sulfate is dissolved in deionized water, 10min systems is stirred with 600 revs/min of speed using magnetic stirring apparatus
Obtain the MnSO that molar concentration is 0.005mol/L4Solution D；
(5) by 60mL MnSO4Solution D is transferred in hydro-thermal sensing kettle, then 0.30g C is set perpendicular to hydro-thermal sensing heating
The magnetic induction line direction of standby middle induction coil is put into, and after kettle is sealed, is placed in hydro-thermal induction heating equipment, with 400KHz sensing
Frequency, to 80 DEG C, and is incubated 3h by room temperature, obtains manganese dioxide/foam carbon/carbon-copper composite material E；
(6) by E respectively with the deionized water and the soft washing of analytically pure absolute ethyl alcohol that temperature is room temperature, then at 80 DEG C
Temperature in dry 6h obtain the manganese dioxide with three-dimensional porous rack-like connectivity structure/foam copper sodium-ion battery self-supporting bear
Pole.
Embodiment 3
(1) by thickness be 1mm self-supporting matrix sheet foam coppers cut rectangle foam copper sheet A, make its a length of 4cm,
A width of 2.5cm；
(2) 0.15g A are immersed in analytically pure acetone and 30min are cleaned with 50KHz frequency ultrasound, then take out A,
Again with deionized water rinsing 3 times B；
(3) 0.15g B are immersed in analytically pure absolute ethyl alcohol, and handled in frequency is 50KHz ultrasound environments
30min, then takes out B and is put into baking oven, and 50min is dried in 80 DEG C of temperature and obtains C；
(4) manganese sulfate is dissolved in deionized water, 30min systems is stirred with 800 revs/min of speed using magnetic stirring apparatus
Obtain the MnSO that molar concentration is 0.005mol/L4Solution D；
(5) by 60mL MnSO4Solution D is transferred in hydro-thermal sensing kettle, then 0.15g C is set perpendicular to hydro-thermal sensing heating
The magnetic induction line direction of standby middle induction coil is put into, and after kettle is sealed, is placed in hydro-thermal induction heating equipment, with 500KHz sensing
Frequency, to 120 DEG C, and is incubated 2h by room temperature, obtains manganese dioxide/foam carbon/carbon-copper composite material E；
(6) by E respectively with the deionized water and the soft washing of analytically pure absolute ethyl alcohol that temperature is room temperature, then 120
DEG C temperature in dry 8h obtain the manganese dioxide with three-dimensional porous rack-like connectivity structure/foam copper sodium-ion battery self-supporting
Negative pole.
Embodiment 4
(1) by thickness be 1mm self-supporting matrix sheet foam coppers cut rectangle foam copper sheet A, make its a length of 4cm,
A width of 2.5cm；
(2) 0.45g A are immersed in analytically pure acetone and 20min are cleaned with 50KHz frequency ultrasound, then take out A,
Again with deionized water rinsing 3 times B；
(3) 0.45g B are immersed in analytically pure absolute ethyl alcohol, and are handled in frequency is 50KHz ultrasound environments
20min, then takes out B and is put into baking oven, and 50min is dried in 80 DEG C of temperature and obtains C；
(4) manganese sulfate is dissolved in deionized water, 30min systems is stirred with 800 revs/min of speed using magnetic stirring apparatus
Obtain the MnSO that molar concentration is 0.01mol/L4Solution D；
(5) by 60mL MnSO4Solution D is transferred in hydro-thermal sensing kettle, then by 0.45gC perpendicular to hydro-thermal induction heating equipment
The magnetic induction line direction of middle induction coil is put into, after kettle is sealed, and is placed in hydro-thermal induction heating equipment, with 600KHz sensing frequency
Rate, to 160 DEG C, and is incubated 1h by room temperature, obtains manganese dioxide/foam carbon/carbon-copper composite material E；
(6) by E respectively with the deionized water and the soft washing of analytically pure absolute ethyl alcohol that temperature is room temperature, then 160
DEG C temperature in dry 10h obtain the manganese dioxide with three-dimensional porous rack-like connectivity structure/foam copper sodium-ion battery from branch
Support negative pole.
Embodiment 5
(1) by thickness be 1mm self-supporting matrix sheet foam coppers cut rectangle foam copper sheet A, make its a length of 4cm,
A width of 2.5cm；
(2) 0.15g A are immersed in analytically pure acetone and 20min are cleaned with 50KHz frequency ultrasound, then take out A,
Again with deionized water rinsing 3 times B；
(3) 0.15g B are immersed in analytically pure absolute ethyl alcohol, and handled in frequency is 50KHz ultrasound environments
20min, then takes out B and is put into baking oven, and 40min is dried in 70 DEG C of temperature and obtains C；
(4) manganese sulfate is dissolved in deionized water, 20min systems is stirred with 700 revs/min of speed using magnetic stirring apparatus
Obtain the MnSO that molar concentration is 0.009mol/L4Solution D；
(5) by 60mL MnSO4Solution D is transferred in hydro-thermal sensing kettle, then 0.15g C is set perpendicular to hydro-thermal sensing heating
The magnetic induction line direction of standby middle induction coil is put into, and after kettle is sealed, is placed in hydro-thermal induction heating equipment, with 500KHz sensing
Frequency, to 100 DEG C, and is incubated 2h by room temperature, obtains manganese dioxide/foam carbon/carbon-copper composite material E；
(6) by E respectively with the deionized water and the soft washing of analytically pure absolute ethyl alcohol that temperature is room temperature, then 100
DEG C temperature in dry 8h obtain the manganese dioxide with three-dimensional porous rack-like connectivity structure/foam copper sodium-ion battery self-supporting
Negative pole.
The self-supporting two-dimensional nanostructure self-supporting negative pole that the present invention is constructed using hydro-thermal induction heating technique original position, to steep
Foam copper is supporter, while electric conductivity is improved, forms three-dimensional porous rack-like connectivity structure, its surface in situ grown two dimension
Nano-manganese dioxide thin slice；The thin slice of nanosizing shortens Na+Diffusion path, foam copper also has certain free space to hold
Expanded by electrode, improve the high rate performance and cycle performance of battery；Porous increases the contact surface of electrode and electrolyte
Product, so as to increase embedding lithium space, improves specific capacity；Porous connection can reduce ohmic internal resistance, beneficial to electric transmission, reduce electric charge
Transfer resistance.
Claims (9)
1. the preparation method of a kind of manganese dioxide/foam copper sodium-ion battery self-supporting negative pole, it is characterised in that including following step
Suddenly：
1) self-supporting matrix sheet foam copper is cut to the foam copper sheet A of rectangle；
2) foam copper sheet A is immersed in after being cleaned by ultrasonic in acetone and obtains B with deionized water rinsing again；
3) B is immersed in absolute ethyl alcohol, and handled in ultrasound environments, then dry C；
4) manganese sulfate is dissolved in deionized water, MnSO is made in stirring4Solution D；
5) by MnSO4Solution D is transferred in hydro-thermal sensing kettle, is put into C, wherein 0.15~0.45g C are added in per 60mLD, kettle is close
It is honored as a queen, is placed in hydro-thermal induction heating equipment, with 400~600KHz induction frequencies by room temperature to 80~160 DEG C, and protects
1~3h of temperature, obtains manganese dioxide/foam carbon/carbon-copper composite material E；
6) manganese dioxide/foam carbon/carbon-copper composite material E is washed with deionized water and absolute ethyl alcohol respectively, being then dried to obtain has
The manganese dioxide of three-dimensional porous rack-like connectivity structure/foam copper sodium-ion battery self-supporting negative pole.
2. a kind of preparation method of manganese dioxide according to claim 1/foam copper sodium-ion battery self-supporting negative pole, its
Be characterised by, step 1) in sheet-formed foam copper thickness be 1mm, foam copper sheet A a length of 4cm, a width of 2.5cm.
3. a kind of preparation method of manganese dioxide according to claim 1/foam copper sodium-ion battery self-supporting negative pole, its
Be characterised by, step 2) in acetone, step 3) in absolute ethyl alcohol and step 6) in absolute ethyl alcohol be analysis it is pure.
4. a kind of preparation method of manganese dioxide according to claim 1/foam copper sodium-ion battery self-supporting negative pole, its
It is characterised by, step 2) the middle frequency that is cleaned by ultrasonic is 50KHz, and the ultrasonic cleaning time is 10~30min.
5. a kind of preparation method of manganese dioxide according to claim 1/foam copper sodium-ion battery self-supporting negative pole, its
Be characterised by, step 3) in ultrasonically treated frequency be 50K Hz, sonication treatment time be 10~30min.
6. a kind of preparation method of manganese dioxide according to claim 1/foam copper sodium-ion battery self-supporting negative pole, its
Be characterised by, step 3) in drying temperature be 60~80 DEG C, the time be 30~50min.
7. a kind of preparation method of manganese dioxide according to claim 1/foam copper sodium-ion battery negative pole, its feature exists
In step 4) in manganese sulfate is dissolved in deionized water, stirring be made 0.005~0.01mol/L MnSO4Solution D, uses magnetic
Power agitator is stirred, and speed is 600~800 revs/min, and the time is 10~30min.
8. a kind of preparation method of manganese dioxide according to claim 1/foam copper sodium-ion battery negative pole, its feature exists
In step 5) in C induction coils in hydro-thermal induction heating equipment magnetic induction line place.
9. a kind of preparation method of manganese dioxide according to claim 1/foam copper sodium-ion battery negative pole, its feature exists
In step 6) in F is washed using deionized water and absolute ethyl alcohol at room temperature, in drying process drying temperature for 80~
160 DEG C, the time is 6~10h.
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| CN113206253A (en) * | 2021-04-29 | 2021-08-03 | 陕西科技大学 | Foam copper potassium ion battery material and preparation method thereof |
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| CN110176602A (en) * | 2019-06-26 | 2019-08-27 | 陕西科技大学 | A kind of preparation process of the long-life sodium-ion battery three-dimensional porous carbon nano-electrode material of phosphorus doping biomass |
| CN110240160A (en) * | 2019-06-26 | 2019-09-17 | 陕西科技大学 | A kind of preparation method of the biomass porous carbon nano-electrode material of sodium-ion battery boron doping |
| CN110299537A (en) * | 2019-06-26 | 2019-10-01 | 陕西科技大学 | A kind of preparation process of the biomass porous carbon nano-electrode material of long circulating lithium ion battery sulfur doping |
| CN110627037A (en) * | 2019-06-26 | 2019-12-31 | 陕西科技大学 | Preparation method of nitrogen-doped biomass porous carbon nano electrode material |
| CN110176602B (en) * | 2019-06-26 | 2020-09-25 | 陕西科技大学 | Preparation process of phosphorus-doped biomass three-dimensional porous carbon nano electrode material for long-life sodium-ion battery |
| CN110240160B (en) * | 2019-06-26 | 2021-03-02 | 陕西科技大学 | Preparation method of boron-doped biomass porous carbon nano electrode material for sodium ion battery |
| CN110627037B (en) * | 2019-06-26 | 2021-07-06 | 陕西科技大学 | Preparation method of nitrogen-doped biomass porous carbon nano electrode material |
| CN113206253A (en) * | 2021-04-29 | 2021-08-03 | 陕西科技大学 | Foam copper potassium ion battery material and preparation method thereof |
| 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 |
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