CN107293761B - A kind of Co@N-C composite positive pole, preparation method and the application in lithium-air battery - Google Patents
A kind of Co@N-C composite positive pole, preparation method and the application in lithium-air battery Download PDFInfo
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Abstract
The invention discloses a kind of Co@N-C composite materials, it is characterised in that: nano cobalt granule is distributed in situ in nitrating carbon ball.The present invention also provides a kind of preparation methods of composite material, will react at lower than 10 DEG C comprising zinc salt, polyvinylpyrrolidone, hexacyanocobaltate acid mixed salt solution, and purifying is stood after, is separated by solid-liquid separation；The solid of separation of solid and liquid is freeze-dried, presoma is obtained；Presoma 800 DEG C or more at a temperature of be carbonized to get.The invention also includes the applications by the composite material in lithium sky battery.Co@N-C composite material made from this method is spherical shape, and being used as lithium-air battery catalyst material has lower overpotential, height ratio capacity and excellent cycle performance, and preparation method is simple, low in cost, has preferable Research Prospects.
Description
Technical field
The present invention relates to the preparation fields of battery material, and in particular to a kind of lithium-air battery catalyst material.
Background technique
People develop simultaneously adds elctro-catalyst in lithium air battery positive electrode material, be in order to utilize its electro-catalysis ability,
To accelerate the slow electrode reaction dynamics of lithium-air battery, to mitigate lithium-air battery serious pole in charge and discharge process
Change phenomenon.The charge and discharge process of lithium-air battery is related to the electrochemical reaction of oxygen, this reaction can be abstracted into hydrogen reduction
(ORR) and two processes of oxygen evolution reaction (OER) are reacted, therefore are actually to enclose to the research of lithium-air battery elctro-catalyst
It is carried out around the electrocatalytic reaction of oxygen.Currently, being developed diversified lithium air battery positive electrode electro-catalysis
Agent material has noble metal catalyst, non-noble metal oxide catalyst, non-oxidized substance catalyst and carbon material catalyst and more
Kind new catalyst etc..
Transition metal has obtained many concerns because its resource is comparatively abundant in recent years, and Fe, Co, Ni, Mn exist
Catalytic field research is very more, including its oxide, sulfide etc., and it shows more excellent catalytic performance.By
Metal/the N/C and metal@N-C that transition metal and carbon and nitrogen are formed are led as a kind of new catalyst in catalysis such as HER and ORR
Domain becomes a hot spot, wherein the Fe@N-C especially formed with transition-metal Fe, Co, Ni, Co@N-C, Ni@N-C are typical generation
Table, wherein the performance of Co@N-C composite material is more excellent.However application report of this composite material on lithium-air battery
It is less.
For example, the Chinese patent literature of Publication No. CN106920964A discloses a kind of prussian blue sodium-ion battery
Positive electrode, the prussian blue sodium-ion battery positive material are replaced in Prussian blue lattice by transition metal element gradient
The intracorporal iron ion of iron nitrogen octahedral, wherein the transition metal element is manganese, any in cobalt, nickel, copper, zinc, and transition metal
Element replaces iron nitrogen in Prussian blue lattice octahedra from Prussian blue intra-die to surface in concentration gradient from low to high
Interior iron ion.The Chinese patent literature of Publication No. CN106898743A discloses similar method.The material of existing method
Material is difficult to obtain good electric property in lithium sky field of batteries.
Summary of the invention
For defect existing for existing lithium-air battery catalyst material, the present invention provides a kind of Co@N-C composite woods
A kind of material, it is desirable to provide material with excellent electric property.
Another object of the present invention is to provide a kind of preparation methods of Co@N-C composite material.
It is a third object of the invention to provide a kind of application of Co@N-C composite material in lithium sky battery.
A kind of Co@N-C composite material, nano cobalt granule are distributed in situ in nitrating carbon ball.
Co@N-C composite material provided by the invention, the Co@N-C composite material is integrally in sphere；Nano particle Co
It is evenly distributed in the inside of porous nitrating carbon ball.
Preferably, the partial size of the Co@N-C composite positive pole is 0.5~2 μm.
Preferably, the specific surface area of the Co@N-C composite positive pole is 200~600m2/g。
Preferably, the partial size of nano Co particle is 50~100nm.
Composite material of the present invention, is porous spherical composite material, and rough surface has biggish specific surface
Product provides more active sites for catalysis reaction, enhances material conductivity, preferably played Co@N-C composite material
Catalytic action, make battery charging and discharging capacity with higher and excellent stable circulation performance.
The present invention also provides the preparation methods of the Co@N-C composite material described in one kind, will include zinc salt, polyethylene pyrrole
Pyrrolidone, hexacyanocobaltate acid salt mixed solution lower than reacting at 10 DEG C, purifying is stood after, is separated by solid-liquid separation；By solid-liquid point
From solid freeze-drying, obtain presoma；Presoma 800 DEG C or more at a temperature of be carbonized to get.
The method of the present invention is originally reacted at a temperature of described using zinc salt and hexacyanocobaltate acid salt, is then cooperated cold
Dry, the obtained zinc/cobalt dual-metal cyanide complex (precursor) of assembling is lyophilized；The zinc/cobalt dual-metal cyanide complex is carried out again
Cobalt@N-C composite material is finally made as sacrificial metal in carbonization treatment, zinc.The present inventor is the study found that use present invention side
Co N-C composite positive pole made from method has excellent electric property.
In addition, the present inventors have additionally discovered that, using the preparation method, the composite wood of pattern spherical in shape can unexpectedly be made
Material；The homogeneity of the material of the pattern is good, and electric property is more excellent.
In the present invention, the zinc salt is preferably Zn2+Water soluble salt.
Further preferably, the zinc salt is at least one of zinc acetate, zinc nitrate, zinc sulfate, preferably zinc acetate.
The hexacyanocobaltate acid salt is at least one of potassium cobalticyanide, cobalt Cymag；Preferably potassium cobalticyanide.
The molar ratio of more preferably scheme, the zinc salt and hexacyanocobaltate acid salt is 1: 1~4: 1.
Further preferably, the molar ratio of the zinc salt and hexacyanocobaltate acid salt is 1: 1~2: 1.
More preferably scheme, the polyvinylpyrrolidonemolecules molecules amount are 5000-60000.
More preferably scheme, the polyvinylpyrrolidone and zinc salt mass ratio are 5: 1~20: 1；Further preferably 5:
1~15: 1.
The inventors discovered that the mixed solution is reacted under the temperature range, can unexpectedly be made
Electric property is excellent and composite material especially suitable for lithium sky battery.
Preferably, reaction temperature is -2~10 DEG C；Further preferably 0~10 DEG C；Most preferably 0~4 DEG C.
In the present invention, in actual mechanical process, preferably by zinc salt, polyvinylpyrrolidone is dissolved in water, forms clear solution；
By hexacyanocobaltate acid salt formation solution soluble in water；The latter is slowly dropped in the former under condition of ice bath, is formed milky
Colloid；Purifying is then stood again, is separated by solid-liquid separation, freeze-drying, and white presoma is obtained；Then, presoma is placed in tubular type
Furnace, carbonization to get.
In the present invention, existing conventional means, such as filtering, centrifugation is can be used in the separation of solid and liquid.The present invention preferably adopts
Use centrifugal method.
Preferred scheme, the standing purification time are 12~48h.
Existing conventional method and existing conventional equipment can be used in freeze-drying method.
Preferred scheme, the sublimation drying are 12~36h.
Preferred scheme, the carburizing temperature are 800~1100 DEG C.
The heating rate of carbonisation is 1~5 DEG C/min.
Under the preferred carburizing temperature, preferred carbonization time is 2~6h.
Preferred scheme, the inert atmosphere are nitrogen or argon atmosphere, preferably argon gas.
The method that lithium-air battery Co@N-C composite material is prepared in technical solution of the present invention mainly passes through at high temperature
Zinc/cobalt dual-metal cyanide complex presoma is managed, sphere material is obtained after carbonization, contains a large amount of Co particle in chondritic,
The fusing point of Zn is lower, evaporates under the high temperature conditions, to form a large amount of hole in bulbous inner part and surface, ultimately forms one
Kind nano particle Co is evenly distributed in the composite material of porous spherical structure.
Co@N-C composite material in the present invention is utilized hexacyanocobaltate acid salt and easily forms zinc/cobalt dual-metal cyanogen with zinc ion
Change complex compound, the nitrogen in cryanide ion is eventually entered in the form of doping in the lattice of carbon, forms defect.In high-temperature process
In lose Zn, form porous Co@N-C composite material.The nano particle of Co@N-C is tightly combined with nitrating carbon, avoids Co
Grain reunion and form bulky grain.Co particle being uniformly distributed in spherical shape makes it have enough catalytic reaction activity sites, than
The lithium peroxide that biggish specific surface area again generates catalysis has enough spaces to adhere to, it is avoided to be covered on catalyst too much
Surface and the performance for seriously affecting catalyst performance are conducive to the cyclical stability for improving lithium-air battery.
The method of nucleocapsid Co@N-C composite material prepared by the present invention comprising the following specific steps
(1) by zinc salt, polyvinylpyrrolidone is dissolved in water, forms clear solution；
(2) by potassium cobalticyanide formation solution soluble in water；
(3) the latter is slowly dropped in the former under condition of ice bath, forms milky colloid, stand purifying for 24 hours~
48h is centrifuged, and freeze-drying obtains white presoma；
(4) presoma is placed in tube furnace, is passed through inert gas in 800 DEG C or more progress high-temperature heat treatments to get Co@N-
C composite.
The present invention also provides Co@N-C composite materials made from the preparation method.
In addition, the invention also includes the applications of the Co@N-C composite material；The Co@N-C composite material is used
Make the positive electrode of lithium sky battery.
Preferably, after mixing the Co@N-C composite material with conductive agent and binder, will be starched in the application
Material is coated on nickel screen, and lithium air battery positive electrode is made.
In the present invention, existing conventional method is can be used in the assemble method of battery, and the conductive agent and binder are also optional
The material that can be recognized with those skilled in the art.
The lithium-air battery performance test methods of Co@N-C composite material prepared by the present invention: weighing above-mentioned material, is added
For 10wt.%Super P as conductive agent, 10wt.% Kynoar (PVDF) is used as binder, ground to be sufficiently added later
A small amount of N-Methyl pyrrolidone (NMP) is mixed to form uniform black paste slurry, and slurry is coated in and is processed through dilute hydrochloric acid
Nickel screen collector on as test electrode, with metal lithium sheet as a comparison electrode assembling become 2032 button cells, use
Electrolyte system is 1M LiTFSI/TEGDME, and the diaphragm used fills used in test loop performance for GF/D fibreglass diaphragm
Discharge current density is 1mA/cm2。
The utility model has the advantages that
1) Co@N-C composite material of the invention with more coarse surface and has pore structure more abundant.It is this
Structure, which is conducive to the lithium peroxide that catalysis generates, has enough spaces to adhere to, and avoids it from being covered on catalyst surface too much and tight
Ghost image rings the performance of catalyst performance, and then is conducive to improve the cyclical stability of lithium-air battery.
2) present invention prepare method of Co@N-C composite material operation is simple and reliable, reproducible, catalytic performance is excellent, has
There are preferable Research Prospects.
3) can be unexpectedly made using the present invention has ball-type pattern and the good composite material of homogeneity, the composite wood
Material has excellent electric property.
Detailed description of the invention
[Fig. 1] is the X-ray diffractogram (XRD) of persursor material made from embodiment 1；
[Fig. 2] is the X-ray diffractogram (XRD) of Co@N-C composite material made from embodiment 1；
[Fig. 3] is the scanning electron microscope (SEM) photograph (SEM) of Co@N-C composite material made from embodiment 1；
[Fig. 4] is the cycle performance figure of the lithium-air battery of the assembling of Co@N-C composite material made from embodiment 1；
[Fig. 5] is the high rate performance figure of the lithium-air battery of the assembling of Co@N-C composite material made from embodiment 1.
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention；And the protection scope of the claims in the present invention
It is not limited by the example.
Embodiment 1
Weigh 6mmol zinc acetate, 11.12g polyvinylpyrrolidone (K30 respectively first；Molecular weight 40000) it is added to and contains
In the beaker for having 200mL water, stirring forms clear solution；It weighs 4mmol potassium cobalticyanide and is dissolved in 200mL water formation clear solution.
The two is placed into 1h in ice water, (0~4 DEG C) stirring under condition of ice bath cooperates ultrasonic wave added, the latter is slowly dropped to the former
In, milky colloid is gradually formed, colloid room temperature is stood into purifying for 24 hours, centrifugation obtains thick white solid, is freeze-dried
For 24 hours to get arrive zinc/cobalt dual-metal cyanide complex presoma.
Appropriate presoma is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas, will be managed
Formula furnace is warming up to 900 DEG C of (heating rate is 2 DEG C/min) heat treatment 4h to get Co@N-C composite material.
Button cell, material knot are assembled into using lithium-air battery Co@N-C composite material manufactured in the present embodiment and lithium
Structure characterization and chemical property are as shown in the figure:
In Fig. 1 contrast standard diffracting spectrum illustrate in presoma without other impurities, be single zinc/cobalt dual-metal cyanogen
Change complex compound Zn3[Co(CN)6]2。
In Fig. 2 contrast standard diffracting spectrum illustrate in Co@N-C composite material without other impurities, be single Co@N-
C composite.
It can be seen that the Co@N-C composite material prepared is uniformly distributed in ball for spherical shape Co particle in Fig. 3, wherein
The size of Co@N-C composite material nanometer Co particle is about 60nm.Specific surface area 465m2/g。
Show the electrode using the production of Co@N-C composite material in Fig. 4, in 4mA/cm2Constant-current discharge density under, circulation
Capacity is decayed after 40 circles, shows good cyclical stability.
Show the electrode using the production of Co@N-C composite material in Fig. 5, respectively in 1,2,4mA/cm2Current density following table
Reveal the specific capacity of 3845,2800,1980mAh/g.
Embodiment 2
Weigh 4mmol zinc acetate respectively first, 11.12g polyvinylpyrrolidone (K30) is added to containing 200mL water
In beaker, stirring forms clear solution；It weighs 4mmol potassium cobalticyanide and is dissolved in 200mL water formation clear solution.The two is placed into ice
1h in water, (0~4 DEG C) stirring under condition of ice bath, cooperates ultrasonic wave added, the latter is slowly dropped in the former, is gradually formed
Colloid room temperature is stood purifying 18h by milky colloid, and centrifugation obtains thick white solid, freeze-drying for 24 hours to get to zinc/
Cobalt dual-metal cyanide complex presoma.
Appropriate presoma is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas, will be managed
Formula furnace is warming up to 1000 DEG C of (heating rate is 2 DEG C/min) heat treatment 2h to get Co@N-C composite material.
The Co@N-C composite material that this method prepares is the inside that Co nano particle is uniformly distributed in ball, wherein Co@
The size of N-C composite material nanometer Co particle is about 80nm.Specific surface area 402m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 4mA/cm2
Constant-current discharge density under, circulation 35 circle after capacity decay.
1、2、4mA/cm2Current density under show the specific capacities of 3600,2453,1602mAh/g.
Embodiment 3
Weigh 6mmol zinc acetate, 11.12g polyvinylpyrrolidone (K29 respectively first；Molecular weight 58000) it is added to and contains
In the beaker for having 200mL water, stirring forms clear solution；It weighs 3mmol potassium cobalticyanide and is dissolved in 200mL water formation clear solution.
The two is placed into 1h in ice water, (0~4 DEG C) stirring under condition of ice bath cooperates ultrasonic wave added, the latter is slowly dropped to the former
In, milky colloid is gradually formed, colloid room temperature is stood into purifying 48h, centrifugation obtains thick white solid, is freeze-dried
18h to get arrive zinc/cobalt dual-metal cyanide complex presoma.
Appropriate presoma is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas, will be managed
Formula furnace is warming up to 900 DEG C of (heating rate is 2 DEG C/min) heat treatment 6h to get Co@N-C composite material.
The Co@N-C composite material that this method prepares is the inside that Co nano particle is uniformly distributed in ball, wherein Co@
The size of N-C composite material nanometer Co particle is about 60nm.Specific surface area 395m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 4mA/cm2
Constant-current discharge density under, circulation 32 circle after capacity decay.
1、2、4mA/cm2Current density under show the specific capacities of 3254,2208,1235mAh/g.
Embodiment 4
Weigh 8mmol zinc acetate respectively first, 11.12g polyvinylpyrrolidone (K29) is added to containing 200mL water
In beaker, stirring forms clear solution；It weighs 2mmol potassium cobalticyanide and is dissolved in 200mL water formation clear solution.The two is placed into ice
1h in water, (0~4 DEG C) stirring under condition of ice bath, cooperates ultrasonic wave added, the latter is slowly dropped in the former, is gradually formed
Colloid room temperature is stood purifying for 24 hours by milky colloid, and centrifugation obtains thick white solid, be freeze-dried 36h to get to zinc/
Cobalt dual-metal cyanide complex presoma.
Appropriate presoma is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas, will be managed
Formula furnace is warming up to 950 DEG C of (heating rate is 2 DEG C/min) heat treatment 2h to get Co@N-C composite material.
The Co@N-C composite material that this method prepares is the inside that Co nano particle is uniformly distributed in ball, wherein Co@
The size of N-C composite material nanometer Co particle is about 70nm.Specific surface area 314m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 4mA/cm2
Constant-current discharge density under, circulation 30 circle after capacity decay.
1、2、4mA/cm2Current density under show the specific capacities of 3008,2102,1089mAh/g.
Embodiment 5
Weigh 6mmol zinc acetate respectively first, 11.12g polyvinylpyrrolidone (K30) is added to containing 200mL water
In beaker, stirring forms clear solution；It weighs 5mmol potassium cobalticyanide and is dissolved in 200mL water formation clear solution.The two is placed into ice
1h in water, (0~4 DEG C) stirring under condition of ice bath, cooperates ultrasonic wave added, the latter is slowly dropped in the former, is gradually formed
Colloid room temperature is stood purifying 20h by milky colloid, and centrifugation obtains thick white solid, be freeze-dried 28h to get to zinc/
Cobalt dual-metal cyanide complex presoma.
Appropriate presoma is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas, will be managed
Formula furnace is warming up to 850 DEG C of (heating rate is 2 DEG C/min) heat treatment 4h to get Co@N-C composite material.
The Co@N-C composite material that this method prepares is the inside that Co nano particle is uniformly distributed in ball, wherein Co@
The size of N-C composite material nanometer Co particle is about 100nm.Specific surface area 256m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 4mA/cm2
Constant-current discharge density under, circulation 29 circle after capacity decay.
1、2、4mA/cm2Current density under show the specific capacities of 2998,2103,1032mAh/g.
Comparative example 1
This comparative example is inquired into, and zinc salt is not added；Concrete operations are as follows:
It weighs 11.12g polyvinylpyrrolidone (K30) respectively first to be added in the beaker containing 200mL water, stirs shape
At clear solution；It weighs 5mmol potassium cobalticyanide and is dissolved in 200mL water formation clear solution.The two is placed into 1h in ice water, in ice bath
Under the conditions of (0~4 DEG C) stirring, cooperate ultrasonic wave added, the latter is slowly dropped in the former, milky colloid is gradually formed,
Colloid room temperature is stood into purifying for 24 hours, centrifugation obtains thick white solid, and freeze-drying is for 24 hours to get arriving zinc/cobalt dual-metal cyaniding
Complex compound presoma.
Appropriate presoma is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas, will be managed
Formula furnace is warming up to 900 DEG C of (heating rate is 2 DEG C/min) heat treatment 4h to get Co@N-C composite material.
The Co@N-C composite material that this method prepares is the inside that Co nano particle is uniformly distributed in ball, surface light
Sliding, hole is insufficient, and wherein the size of Co@N-C composite material nanometer Co particle is about 60nm.Specific surface area is 82m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 4mA/cm2
Constant-current discharge density under, circulation 25 circle after capacity decay.
1、2、4mA/cm2Current density under show the specific capacities of 2564,1882,864mAh/g.
Comparative example 2
This comparative example is inquired into, and is reacted under normal temperature conditions；Concrete operations are as follows:
Weigh 6mmol zinc acetate respectively first, 11.12g polyvinylpyrrolidone (K30) is added to containing 200mL water
In beaker, stirring forms clear solution；It weighs 5mmol potassium cobalticyanide and is dissolved in 200mL water formation clear solution.The two is placed normal
(20~25 DEG C) stirrings under the conditions of temperature, cooperate ultrasonic wave added, the latter are slowly dropped in the former, milky glue is gradually formed
Colloid room temperature is stood purifying for 24 hours by body, and centrifugation obtains thick white solid, and freeze-drying is for 24 hours to get arriving zinc/cobalt dual-metal cyanogen
Change complex compound presoma.
Appropriate presoma is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas, will be managed
Formula furnace is warming up to 900 DEG C of (heating rate is 2 DEG C/min) heat treatment 4h to get Co@N-C composite material.
The pattern that the Co@N-C composite material that this method prepares is not fixed, more in a jumble, wherein Co@N-C is compound
The size of material nano Co particle is about 150nm.Specific surface area 248m2/g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 4mA/cm2
Constant-current discharge density under, circulation 20 circle after capacity decay.
1、2、4mA/cm2Current density under show the specific capacities of 2403,1346,524mAh/g.
Comparative example 3
This comparative example is inquired into, and polyvinylpyrrolidone is not added；Concrete operations are as follows:
It weighs 6mmol zinc acetate first to be added in the beaker containing 200mL water, stirring forms clear solution；It weighs
4mmol potassium cobalticyanide is dissolved in 200mL water and forms clear solution.The two is placed into 1h in ice water, under condition of ice bath (0~4 DEG C)
Stirring cooperates ultrasonic wave added, the latter is slowly dropped in the former, milky colloid is gradually formed, colloid room temperature is stood
For 24 hours, centrifugation obtains thick white solid for purifying, and freeze-drying is for 24 hours to get arriving zinc/cobalt dual-metal cyanide complex presoma.
Appropriate presoma is weighed, is put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace.It is passed through argon gas, will be managed
Formula furnace is warming up to 900 DEG C of (heating rate is 2 DEG C/min) heat treatment 4h to get Co@N-C composite material.
The Co@N-C composite material that this method prepares is that Co nano particle is distributed in the inside of ball, rough surface,
Grain is intensive, and carbon content is insufficient, and wherein the size of Co@N-C composite material nanometer Co particle is about 90nm.Specific surface area is 56m2/
g。
Button cell is assembled into using lithium-air battery catalyst material manufactured in the present embodiment and lithium piece, in 4mA/cm2
Constant-current discharge density under, circulation 15 circle after capacity decay.
1、2、4mA/cm2Current density under show the specific capacities of 1988,986,462mAh/g.
Claims (11)
1. a kind of Co@N-C composite material, it is characterised in that: nano cobalt granule is distributed in situ in nitrating carbon ball；
The preparation process of Co@N-C composite material are as follows: will exist comprising zinc salt, polyvinylpyrrolidone, hexacyanocobaltate acid mixed salt solution
It is reacted at lower than 10 DEG C, purifying is stood after, is separated by solid-liquid separation；The solid of separation of solid and liquid is freeze-dried, presoma is obtained；Before
Drive body 800 DEG C or more at a temperature of be carbonized to get.
2. Co@N-C composite material according to claim 1, it is characterised in that: the Co@N-C composite positive pole
Partial size is 0.5 ~ 2 μm；Specific surface area is 200 ~ 600 m2/ g, wherein the partial size of nano Co particle is 50 ~ 100 nm.
3. Co@N-C composite material according to claim 1, it is characterised in that: the hexacyanocobaltate acid salt is cobalt cyaniding
At least one of potassium, cobalt Cymag；
The zinc salt is at least one of zinc acetate, zinc nitrate, zinc sulfate.
4. Co@N-C composite material according to claim 1 or 3, it is characterised in that: the zinc salt and hexacyanocobaltate acid salt
Molar ratio is 1:1 ~ 4:1.
5. Co@N-C composite material according to claim 1, it is characterised in that: reaction temperature is 0 ~ 10oC。
6. Co@N-C composite material according to claim 1, it is characterised in that: the polyvinylpyrrolidonemolecules molecules amount is
5000-60000；The polyvinylpyrrolidone and zinc salt mass ratio are 5:1 ~ 20:1.
7. Co@N-C composite material according to claim 1, it is characterised in that: the standing purification time is 12 ~ 48 h,
The sublimation drying is 12 ~ 36 h.
8. Co@N-C composite material according to claim 1, it is characterised in that: carburizing temperature is 800 ~ 1100oC。
9. Co@N-C composite material according to claim 8, it is characterised in that: carbonization time is 2 ~ 6 h.
10. the application of -9 described in any item Co@N-C composite materials according to claim 1, it is characterised in that: be used as the empty electricity of lithium
The positive electrode in pond.
11. the application of Co@N-C composite material according to claim 10, it is characterised in that: by the Co@N-C composite wood
After material is mixed with conductive agent and binder, slurry is coated on nickel screen, lithium air battery positive electrode is made.
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| CN112960663B (en) * | 2021-02-02 | 2023-11-24 | 深圳赛骄阳能源科技股份有限公司 | LiFe X Co 1-X PO 4 Preparation method of/N-C/CC composite material |
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| CN114142049B (en) * | 2021-11-26 | 2024-06-07 | 武汉科思特仪器股份有限公司 | Preparation method and application of hollow carbon-based oxygen reduction electrocatalyst |
| CN114597427A (en) * | 2022-03-10 | 2022-06-07 | 合肥工业大学智能制造技术研究院 | Preparation method and application of nitrogen-doped carbon-coated cobaltosic oxide @ cobalt non-noble metal oxygen reduction catalyst |
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