CN106558689A - A kind of electrochemical in-situ method prepares the method for two-arch tunnel hybrid metal selenides and its application - Google Patents
A kind of electrochemical in-situ method prepares the method for two-arch tunnel hybrid metal selenides and its application Download PDFInfo
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Abstract
The invention discloses class co-continuous CoSe2/NiSe2Nano composite material and preparation method and application.Co-continuous CoSe provided by the present invention2/NiSe2Nano composite material has outstanding storage sodium performance, is an excellent anode material of lithium-ion battery.It is simply novel for the preparation method of the nano composite material, can be mass, raw material is easy to get, and shows good using value.More importantly, in this method, presoma has reached the uniform compound of molecular level, the nano composite material of the compound and its uniform co-continuous for being formed by electrochemical process in situ again, so as to avoid biphase compound uneven, discontinuous shortcoming in conventional composite thing preparation process.Co-continuous CoSe2/NiSe2Nano composite material is used as to illustrate outstanding high rate performance and cycle performance during anode material of lithium-ion battery.
Description
Technical field
The invention belongs to nano material and sodium-ion battery technical field, are related to a kind of two-arch tunnel hybrid metal selenides
Electrochemical in-situ preparation method and its application in anode material of lithium-ion battery.
Background technology
The advantages of lithium ion battery is due to high-energy-density, safety and stability, green high-efficient, memory-less effect becomes
Energy storage device of greatest concern.At present, all kinds of portable electric appts, electric vehicle, storage are had been widely used for
The fields such as energy equipment.But due to the resource of lithium in the earth's crust it is relatively limited, with electrokinetic cell and extensive energy storage to lithium from
Increasing considerably for the demand of sub- battery, it is following to face the lithium resource shortage problem of sternness.For comparing, sodium is on earth
Reserves extremely enrich, and sodium-ion battery is similar to the energy storage mechnism of lithium ion battery, therefore causes the extensive of people
Concern, becomes most potential candidate after both lithium ion batteries.But as sodium ion radius is more than lithium ion, therefore
Cause the negative material graphite of Current commercial directly apply to sodium-ion battery, therefore find suitable sodium-ion battery
Negative material is extremely urgent.Metal selenide is due to having higher theoretical specific capacity, and tap density is very high, becomes one
The very promising anode material of lithium-ion battery of class.But the selenides limited capacity of the single metal generally studied, therefore send out
The composite of two kinds of metal selenides of exhibition becomes and can obtain the effective of outstanding storage sodium performance with reference to the advantage of bi-material
Method.However, common complex method is often difficult to realize uniformly being combined, good effect is not reached.So being badly in need of development
A kind of method that can realize that two kinds of selenides are uniformly compound.
Here, we have synthesized a kind of monodispersed CoNiSe of regular appearance first by solvent thermal design4Double gold
Category selenides solid-solution material (cube pattern, the length of side about 270nm are internal for spherical secondary structure, diameter 45-65nm), then
Such a co-continuous CoSe are obtained by electrochemical process (constant current charge-discharge) in situ2/NiSe2Metal nanometer composite material
(co-continuous metal selenide refers to the biphase completely continuous of two kinds of different metal selenides).The bimetallic obtained by the method
In selenides composite, two kinds of metals have reached the compound and very homogeneous of molecular level, and regular appearance, controllable are answered
For sodium-ion battery negative material when show high power capacity, excellent cyclical stability and high rate performance.
The content of the invention
The purpose of the present invention is to propose to by electrochemical in-situ method, a kind of realize that co-continuous metal selenide nanometer is answered
Condensation material (CoSe2/NiSe2) controllable standby new approaches and have studied its application in sodium-ion battery.
Co-continuous metal selenide nano composite material CoSe that the present invention is provided2/NiSe2, by CoNiSe4Bimetallic selenium
Compound solid-solution material (micro-nano compound structure) is obtained by electrochemical method in situ.
Concrete grammar is as follows：
(1) by certain mol proportion example by CoSO4·7H2O and NiSO4·6H2O is added to the water stirring to being completely dissolved.
(2) ethanol is added in the solution that step (1) is obtained, add selenium powder, be sufficiently stirred for,.
(3) hydrazine hydrate is added in the solution that step (2) is obtained, ultrasonic agitation is uniform afterwards.
(4) solution that step (3) is obtained is transferred in teflon-lined kettle, carries out solvent thermal reaction.
(5) the product pressed powder that collection step (3) is obtained, is washed and is dried.
(6) by the CoNiSe for obtaining4Nano composite material presses 7 with acetylene black, sodium carboxymethyl cellulose:2:1 ratio, with
Water is that slurry is uniformly made in solvent grinding, is coated uniformly on Copper Foil.After to be dried as battery working electrode, with gold
Category sodium piece carries out constant current charge-discharge on LAND as being assembled in glove box to electrode after button half-cell.Voltage range
For 0.01-2.8V.Through the constant current charge-discharge circulation of a circle, what is obtained is exactly co-continuous CoSe2/NiSe2Nano composite material.
Wherein, the CoSO described in step (1)4·7H2O and NiSO4·6H2The ratio of O can be 1:9-9:1.
In step (2), amount of alcohol added can be 5-15mL.
In step (4), the time of solvent thermal reaction can be 6-24h, and the temperature of reaction can be 160-200 DEG C
Description of the drawings
Fig. 1 is CoNiSe in embodiment 54The XRD figure of solid-solution material.
Fig. 2 is CoNiSe in embodiment 54The electron scanning micrograph of solid-solution material.
Fig. 3 is the CoNiSe in embodiment 54The pattern and its formation co-continuous CoSe of solid-solution material2/NiSe2Nanometer is multiple
The schematic diagram of condensation material.
Fig. 4 is co-continuous CoSe in embodiment 52/NiSe2When nano composite material is as anode material of lithium-ion battery
Charging and discharging curve figure.
Fig. 5 is co-continuous CoSe in embodiment 52/NiSe2When nano composite material is as anode material of lithium-ion battery
High rate performance.
Fig. 6 is co-continuous CoSe in embodiment 52/NiSe2Nano composite material is used as during anode material of lithium-ion battery
Cycle performance.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
Prepare co-continuous metal selenide nano composite material CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O presses 3:7(0.6mmol:1.4mmol) mol ratio is stirred in being added to 44mL water
Mix to being completely dissolved, backward solution in add 10mL ethanol, add 4mmol selenium powders, be sufficiently stirred for.It is eventually adding 16mL water
Close hydrazine, ultrasonic agitation 0.5h.
Then the solution for obtaining is transferred in teflon-lined kettle, solvent thermal reaction is carried out at 160 DEG C, instead
It is 6h between seasonable.Collect reaction and obtain pressed powder (Co0.3Ni0.7Se4), washed and be dried.
By the Co for obtaining0.3Ni0.7Se4Nano composite material presses 7 with acetylene black, sodium carboxymethyl cellulose:2:1 ratio,
Slurry is uniformly made by solvent grinding of water, is coated uniformly on Copper Foil.After to be dried as battery working electrode, with
Metallic sodium piece carries out constant current charge-discharge on blue electric tester as being assembled in glove box to electrode after button half-cell.
Voltage range is 0.01-2.8V.Through the circulation of a circle, what is obtained is exactly co-continuous CoSe2/NiSe2Nano composite material.
Embodiment 2
Prepare co-continuous metal selenide nano composite material CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O presses 5:5(1mmol:1mmol) mol ratio stir in being added to 44mL water to
Be completely dissolved, backward solution in add 10mL ethanol, add 4mmol selenium powders, be sufficiently stirred for.It is eventually adding 16mL hydrations
Hydrazine, ultrasonic agitation 0.5h.Then the solution for obtaining is transferred in teflon-lined kettle, solvent is carried out at 160 DEG C
Thermal response, response time are 6h.Collect reaction and obtain pressed powder (CoNiSe4), washed and be dried.
By the CoNiSe for obtaining4Nano composite material presses 7 with acetylene black, sodium carboxymethyl cellulose:2:1 ratio, with water
Slurry is uniformly made for solvent grinding, is coated uniformly on Copper Foil.After to be dried as battery working electrode, with metal
Sodium piece carries out constant current charge-discharge on blue electric tester as being assembled in glove box to electrode after button half-cell.Voltage
Interval is 0.01-2.8V.Through the circulation of a circle, what is obtained is exactly co-continuous CoSe2/NiSe2Nano composite material.
Embodiment 3
Prepare co-continuous metal selenide nano composite material CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O presses 5:5(0.2mmol:1.8mmol) mol ratio is stirred in being added to 44mL water
Mix to being completely dissolved, backward solution in add 5mL ethanol, add 4mmol selenium powders, be sufficiently stirred for.It is eventually adding 16mL water
Close hydrazine, ultrasonic agitation 0.5h.Then the solution for obtaining is transferred in teflon-lined kettle, is carried out at 160 DEG C molten
Agent thermal response, response time are 6h.Collect reaction and obtain pressed powder (CoNiSe4), washed and be dried.
By the CoNiSe for obtaining4Nano composite material presses 7 with acetylene black, sodium carboxymethyl cellulose:2:1 ratio, with water
Slurry is uniformly made for solvent grinding, is coated uniformly on Copper Foil.After to be dried as battery working electrode, with metal
Sodium piece carries out constant current charge-discharge on blue electric tester as being assembled in glove box to electrode after button half-cell.Voltage
Interval is 0.01-2.8V.Through the circulation of a circle, what is obtained is exactly co-continuous CoSe2/NiSe2Nano composite material.
Embodiment 4
Prepare co-continuous metal selenide nano composite material CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O presses 5:5(1mmol:1mmol) mol ratio stir in being added to 44mL water to
Be completely dissolved, backward solution in add 5mL ethanol, add 4mmol selenium powders, be sufficiently stirred for.16mL hydrazine hydrates are eventually adding,
Ultrasonic agitation 0.5h.Then the solution for obtaining is transferred in teflon-lined kettle, solvent thermal is carried out at 180 DEG C anti-
Should, the response time is 6h.Collect reaction and obtain pressed powder (CoNiSe4), washed and be dried.
By the CoNiSe for obtaining4Nano composite material presses 7 with acetylene black, sodium carboxymethyl cellulose:2:1 ratio, with water
Slurry is uniformly made for solvent grinding, is coated uniformly on Copper Foil.After to be dried as battery working electrode, with metal
Sodium piece carries out constant current charge-discharge on blue electric tester as being assembled in glove box to electrode after button half-cell.Voltage
Interval is 0.01-2.8V.Through the circulation of a circle, what is obtained is exactly co-continuous CoSe2/NiSe2Nano composite material.
Embodiment 5
Prepare co-continuous metal selenide nano composite material CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O presses 5:5(1mmol:1mmol) mol ratio stir in being added to 44mL water to
Be completely dissolved, backward solution in add 5mL ethanol, add 4mmol selenium powders, be sufficiently stirred for.16mL hydrazine hydrates are eventually adding,
Ultrasonic agitation 0.5h.Then the solution for obtaining is transferred in teflon-lined kettle, solvent thermal is carried out at 180 DEG C anti-
Should, the response time is 12h.Collect reaction and obtain pressed powder (CoNiSe4), washed and be dried.
By the CoNiSe for obtaining4Nano composite material presses 7 with acetylene black, sodium carboxymethyl cellulose:2:1 ratio, with water
Slurry is uniformly made for solvent grinding, is coated uniformly on Copper Foil.After to be dried as battery working electrode, with metal
Sodium piece carries out constant current charge-discharge on blue electric tester as being assembled in glove box to electrode after button half-cell.Voltage
Interval is 0.01-2.8V.Through the circulation of a circle, what is obtained is exactly co-continuous CoSe2/NiSe2Nano composite material.
Embodiment 6
Prepare co-continuous metal selenide nano composite material CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O presses 7:3(1.4mmol:0.6mmol) mol ratio is stirred in being added to 44mL water
Mix to being completely dissolved, backward solution in add 5mL ethanol, add 4mmol selenium powders, be sufficiently stirred for.It is eventually adding 16mL water
Close hydrazine, ultrasonic agitation 0.5h.Then the solution for obtaining is transferred in teflon-lined kettle, is carried out at 180 DEG C molten
Agent thermal response, response time are 12h.Collect reaction and obtain pressed powder (Co0.7Ni0.3Se4), washed and be dried.
By the Co for obtaining0.7Ni0.3Se4Nano composite material presses 7 with acetylene black, sodium carboxymethyl cellulose:2:1 ratio,
Slurry is uniformly made by solvent grinding of water, is coated uniformly on Copper Foil.After to be dried as battery working electrode, with
Metallic sodium piece carries out constant current charge-discharge on blue electric tester as being assembled in glove box to electrode after button half-cell.
Voltage range is 0.01-2.8V.Through the circulation of a circle, what is obtained is exactly co-continuous CoSe2/NiSe2Nano composite material.
Embodiment 7
Prepare co-continuous metal selenide nano composite material CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O presses 7:3(1.4mmol:0.6mmol) mol ratio is stirred in being added to 44mL water
Mix to being completely dissolved, backward solution in add 5mL ethanol, add 4mmol selenium powders, be sufficiently stirred for.It is eventually adding 16mL water
Close hydrazine, ultrasonic agitation 0.5h.Then the solution for obtaining is transferred in teflon-lined kettle, is carried out at 180 DEG C molten
Agent thermal response, response time are 24h.Collect reaction and obtain pressed powder (Co0.7Ni0.3Se4), washed and be dried.
By the Co for obtaining0.7Ni0.3Se4Nano composite material presses 7 with acetylene black, sodium carboxymethyl cellulose:2:1 ratio,
Slurry is uniformly made by solvent grinding of water, is coated uniformly on Copper Foil.After to be dried as battery working electrode, with
Metallic sodium piece carries out constant current charge-discharge on blue electric tester as being assembled in glove box to electrode after button half-cell.
Voltage range is 0.01-2.8V.Through the circulation of a circle, what is obtained is exactly co-continuous CoSe2/NiSe2Nano composite material.
Embodiment 8
Prepare co-continuous metal selenide nano composite material CoSe2/NiSe2
By CoSO4·7H2O and NiSO4·6H2O presses 1:9(0.2mmol:1.8mmol) mol ratio is stirred in being added to 44mL water
Mix to being completely dissolved, backward solution in add 5mL ethanol, add 4mmol selenium powders, be sufficiently stirred for.It is eventually adding 16mL water
Close hydrazine, ultrasonic agitation 0.5h.Then the solution for obtaining is transferred in teflon-lined kettle, is carried out at 180 DEG C molten
Agent thermal response, response time are 24h.Collect reaction and obtain pressed powder (Co0.1Ni0.9Se4), washed and be dried.
By the Co for obtaining0.1Ni0.9Se4Nano composite material presses 7 with acetylene black, sodium carboxymethyl cellulose:2:1 ratio,
Slurry is uniformly made by solvent grinding of water, is coated uniformly on Copper Foil.After to be dried as battery working electrode, with
Metallic sodium piece carries out constant current charge-discharge on blue electric tester as being assembled in glove box to electrode after button half-cell.
Voltage range is 0.01-2.8V.Through the circulation of a circle, what is obtained is exactly co-continuous CoSe2/NiSe2Nano composite material.
As can be seen from the table, co-continuous CoSe that prepared by the present invention2/NiSe2Nano composite material has outstanding storage sodium
Performance, and method is simple.The composite obtained using the present invention is compound and its uniform, with co-continuous characteristic.
The CoNiSe obtained by example 54Solid-solution material carries out powder X-ray diffraction, and (Rigaku DmaxrB, CuK α is penetrated
Line) test, as a result as shown in figure 1, the diffraction peak of material is in CoSe2With NiSe2Between, it was demonstrated that we successfully synthesize
CoNiSe4Solid-solution material.Electron scanning micrographs of the Fig. 2 (a, b) for embodiment 5, can be from figure finding out embodiment 5
The CoNiSe for obtaining4Solid-solution material is the square micro-nano structure being assembled into by little particle, size uniform, and the square length of side is about
For 270nm, their diameter of secondary structure granule is constituted between 25-50nm.Fig. 3 is CoNiSe in embodiment 54Solid solution
Material forms co-continuous CoSe by electrochemical in-situ method2/NiSe2The change procedure schematic diagram of nano composite material, first
During secondary sodium, CoNiSe4Solid solution combines sodium and electronics, generates metal simple-substance Co, metal simple-substance Ni and Na2Se structures such as Fig. 3
C shown in (), this process is irreversible, and when sodium is gone, sodium and electronics abjection have just obtained the co-continuous of Fig. 3 (d)
CoSe2/NiSe2Composite construction, this process are high reversibles, so in subsequent cyclic process, reaction is only in Co/
NaSe2The CoSe of/Ni and co-continuous2/NiSe2Between be repeated.Fig. 4 is co-continuous CoSe in embodiment 52/NiSe2Nanometer is multiple
Condensation material is used as charging and discharging curve figure during anode material of lithium-ion battery, it can be seen that except first lap discharge curve it
Outward, the charging and discharging curve of 2-5 circles is almost completely superposed, and this also demonstrates the CoSe of co-continuous2/NiSe2Composite construction is outstanding
The reversibility for going out and stability.Fig. 5 and Fig. 6 is respectively the CoSe of co-continuous in embodiment 52/NiSe2It is negative as sodium-ion battery
High rate performance and cycle performance figure during the material of pole.As can be seen from the figure material specific capacity under the electric current density of 50mA/g reaches
To 443mAh/g, even if under the high current density of 5A, capacity is also up to 330mAh/g, the Jing under the ionization density of 600mA/g
After crossing 100 circulations, capability retention also has 90%.To sum up, the CoSe of co-continuous2/NiSe2Nano composite material as sodium from
The negative pole of sub- battery shows excellent high rate performance and cycle performance, and it is special that this has benefited from co-continuous special in its structure
Property.
Claims (8)
1. class co-continuous CoSe2/NiSe2Nano composite material, it is characterised in that nanorize, biphase completely continuous, composite pole
Which is equal, with outstanding storage sodium performance.
2. according to claim 1, the CoSe2/NiSe2The architectural feature of nano composite material is, by CoNiSe4Solid solution
Body material is obtained, CoNiSe4Solid solution generally square micro-nano structure pattern, size uniform, the square length of side are 200-
300nm, preferred 270nm, constitute their diameter of secondary structure granule between 25-50nm.
3. one kind prepares co-continuous CoSe2/NiSe2The method of nano composite material：Characterized in that, with CoSO4·7H2O、
NiSO4·6H2O, selenium powder, water, ethanol, hydrazine hydrate are raw material, by the metal selenizing of the electrochemical method co-continuous for preparing in situ
Thing nano composite material (two kinds of different materials are biphase completely continuous).
A kind of co-continuous CoSe2/NiSe2The preparation method of nano composite material, concrete grammar are as follows：
(1) by certain mol proportion example by CoSO4·7H2O and NiSO4·6H2O is added to the water stirring to being completely dissolved.
(2) ethanol is added in the solution that step (1) is obtained, add selenium powder, be sufficiently stirred for,.
(3) hydrazine hydrate is added in the solution that step (2) is obtained, ultrasonic agitation is uniform afterwards.
(4) solution that step (3) is obtained is transferred in teflon-lined kettle, carries out solvent thermal reaction.
(5) the product pressed powder that collection step (3) is obtained, is washed and is dried, obtained CoNiSe4Solid-solution material.
(6) to CoNiSe4Smear is carried out, discharge and recharge after packed battery obtains co-continuous CoSe2/NiSe2Nano composite material.
4. the CoSO in preparation method according to claim 3, described in step (1)4·7H2O and NiSO4·6H2The ratio of O
Example can be 1:9-9:1.It is preferred that 5:5.
5., in preparation method according to claim 3, in step (2), amount of alcohol added can be 5-15mL, preferred 5mL.
6., in preparation method according to claim 3, in step (4), the time of solvent thermal reaction can be 6-24h, preferably
12h。
7., in preparation method according to claim 3, in step (4), the temperature of solvent thermal reaction can be 160-200 DEG C, excellent
Select 180 DEG C.
8. in the preparation method according to claim 1-7, co-continuous CoSe2/NiSe2Nano composite material is in sodium ion
Application in cell negative electrode material.
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| CN108550806A (en) * | 2018-03-28 | 2018-09-18 | 中南大学 | A kind of MnSe/CoSe2Composite material and preparation method and application |
| CN108554426A (en) * | 2018-03-30 | 2018-09-21 | 深圳华中科技大学研究院 | The difunctional two cobaltous selenides material of one kind and its preparation and application |
| CN108892111A (en) * | 2018-06-22 | 2018-11-27 | 北京大学 | The bimetallic selenides Fe of porous structure2CoSe4Material and its preparation method and application |
| CN109768236A (en) * | 2019-02-22 | 2019-05-17 | 肇庆市华师大光电产业研究院 | A kind of preparation method of the anode material of lithium-ion battery of bimetallic selenides |
| CN111939945A (en) * | 2020-08-20 | 2020-11-17 | 安阳师范学院 | CoSe2NiSe2Preparation of-CC composite material and application of electrolytic water hydrogen evolution performance thereof |
| CN112018361A (en) * | 2020-08-31 | 2020-12-01 | 华中科技大学 | Carbon cloth loaded carbon coated cobalt selenide nanosheet battery cathode material and preparation thereof |
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| CN107311119A (en) * | 2017-06-27 | 2017-11-03 | 武汉理工大学 | Hollow nanoprisms material of the cobalt nickel of four selenizing two and its preparation method and application |
| CN107311119B (en) * | 2017-06-27 | 2020-01-14 | 武汉理工大学 | Hollow nanometer prism material of nickel cobalt diselenide, preparation method and application thereof |
| CN108550806A (en) * | 2018-03-28 | 2018-09-18 | 中南大学 | A kind of MnSe/CoSe2Composite material and preparation method and application |
| CN108550806B (en) * | 2018-03-28 | 2020-10-09 | 中南大学 | MnSe/CoSe2Composite material and preparation method and application thereof |
| CN108554426A (en) * | 2018-03-30 | 2018-09-21 | 深圳华中科技大学研究院 | The difunctional two cobaltous selenides material of one kind and its preparation and application |
| CN108554426B (en) * | 2018-03-30 | 2020-07-28 | 深圳华中科技大学研究院 | Difunctional cobalt diselenide material and preparation and application thereof |
| CN108892111A (en) * | 2018-06-22 | 2018-11-27 | 北京大学 | The bimetallic selenides Fe of porous structure2CoSe4Material and its preparation method and application |
| CN108892111B (en) * | 2018-06-22 | 2020-09-08 | 北京大学 | Bimetallic selenide Fe of porous structure2CoSe4Material, preparation method and application thereof |
| CN109768236A (en) * | 2019-02-22 | 2019-05-17 | 肇庆市华师大光电产业研究院 | A kind of preparation method of the anode material of lithium-ion battery of bimetallic selenides |
| CN109768236B (en) * | 2019-02-22 | 2020-10-20 | 肇庆市华师大光电产业研究院 | Preparation method of sodium ion battery anode material of double-metal selenide |
| CN111939945A (en) * | 2020-08-20 | 2020-11-17 | 安阳师范学院 | CoSe2NiSe2Preparation of-CC composite material and application of electrolytic water hydrogen evolution performance thereof |
| CN112018361A (en) * | 2020-08-31 | 2020-12-01 | 华中科技大学 | Carbon cloth loaded carbon coated cobalt selenide nanosheet battery cathode material and preparation thereof |
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