CN107768645A - A kind of porous nitrogen-doped carbon nanometer sheet composite negative pole material and preparation method thereof - Google Patents

A kind of porous nitrogen-doped carbon nanometer sheet composite negative pole material and preparation method thereof Download PDF

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CN107768645A
CN107768645A CN201710993751.1A CN201710993751A CN107768645A CN 107768645 A CN107768645 A CN 107768645A CN 201710993751 A CN201710993751 A CN 201710993751A CN 107768645 A CN107768645 A CN 107768645A
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negative pole
doped carbon
nanometer sheet
nitrogen
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李莉萍
张丹
徐兴良
李广社
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Jilin University
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Abstract

The invention belongs to technical field of lithium ion, disclose a kind of porous nitrogen-doped carbon nanometer sheet composite negative pole material and preparation method thereof, non-ionic polyacrylamide is added in deionized water, it is completely dissolved under rear stirring condition and adds ferric nitrate, obtained mixed solution heating water bath is to thick, drying, the product after drying are calcined, are finally washed with deionized to obtain product under an inert atmosphere.Fe made from preparation method provided by the invention4N/Fe2O3Nitrogen-doped carbon nanometer sheet composite negative pole material porous/Fe has preferable cyclical stability and high rate performance, and synthetic method is simple, and cost is relatively low, is expected to turn into the novel anode material that a kind of scale uses.

Description

A kind of porous nitrogen-doped carbon nanometer sheet composite negative pole material and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of porous nitrogen-doped carbon nanometer sheet composite negative pole Material and preparation method thereof.Wherein, porous nitrogen-doped carbon nanometer sheet composite negative pole material is new Fe4N/Fe2O3/ Fe is porous Nitrogen-doped carbon nanometer sheet composite negative pole material.
Background technology
Lithium ion battery is due to having the advantages that higher energy density, less environmental pollution and long lifespan, quilt at present Most promising energy accumulating device is considered in mancarried electronic aid.With the development of society, need more power density With the ion battery of energy density, and commercialized graphite cathode can not meet to require.In order to meet the need of social development Ask, scientists make great efforts to explore advanced substitute to substitute graphite cathode.In recent years, transition metal oxide was shown Higher capacity (being about 2-3 times of graphite) causes the attention of scientists.Unfortunately, poor electrical conductivity and fill The problem of larger Volume Changes are still very serious in discharge process, these problems limit their application.
Transition metal nitride has higher electrical conductivity and electro-chemical activity, as a kind of new, promising lithium from Sub- cell negative electrode material appears in scientist at the moment.In these transition metal nitrides, because iron has, nontoxic, content is rich The advantages that rich, relatively low price, its nitride shows big advantage as lithium cell cathode material.However, iron Nitride as negative material due to its larger Volume Changes capacity attenuation in electrochemical reaction process quickly, limit Its practical application.
At present, two kinds of strategies solve the problems, such as above.A kind of method is that the particle size for reducing electrode active material arrives Nanometer.The less particle size of active material can shorten lithium ion diffusion path and increase lithium ion kinetics of diffusion, so as to Effectively reduce Volume Changes.Another method is that active material is compound with carbon material, and it is swollen that carbon material can not only suppress volume It is swollen, electrical conductivity can also be further improved, so as to improve chemical property.But due to current synthesizing nitride method very Limited (J.Mater.Chem.A 3 (2015) 1364-1387), directly synthesize the nitride and carbon materials of the iron of smaller particle size Expect that composite is highly difficult.Recently, scientist reports the Fe grown in graphene oxide2N@C microballoons (Chem.Eur.J.21 (2015) 3249-3256) and the Fe for growing the binder free on carbon cloth2N nano particles (Nano Energy 11 (2015) 348-355) lithium cell negative pole material is used as, show preferable lithium electrical property.But their synthesis Method is all more complicated, and product is required for calcining under the conditions of ammonia and can just obtained.It is well known that ammonia easily make by leakage Into danger, and a large amount of unreacted ammonias can cause environmental pollution, and these are all unfavorable for large-scale production very much.Therefore, invent A kind of simple, at a low price, green method is made to synthesize the composite of the nitride of the iron with smaller particle size and carbon Become particularly important for lithium cell negative pole material.
In summary, the problem of prior art is present be：
Prior art synthetic method is all more complicated, and product is required for calcining under the conditions of ammonia and can just obtained；And And largely unreacted ammonia can cause environmental pollution to prior art, be unfavorable for large-scale production；Prior art products obtained therefrom is steady Qualitative and high rate performance is poor.
The content of the invention
The problem of existing for prior art, the invention provides a kind of porous nitrogen-doped carbon nanometer sheet composite negative pole material Material and preparation method thereof.
The present invention is achieved in that a kind of preparation method of porous nitrogen-doped carbon nanometer sheet composite negative pole material, institute Stating the preparation method of porous nitrogen-doped carbon nanometer sheet composite negative pole material includes：
Step 1, non-ionic polyacrylamide is dissolved in deionized water, Fe(NO3)39H2O is added under stirring condition Stir, stirred under 90 DEG C of water bath conditions to thick；
Step 2, then dry in an oven, dried sample is handled in argon gas atmosphere；
Step 3, products obtained therefrom deionized water ultrasound and filtering and washing, the sample after washing are dried in vacuum drying oven, Obtain porous nitrogen-doped carbon nanometer sheet composite negative pole material.
Further, in step 1, specifically include：1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters In, 0.75g Fe(NO3)39H2Os are added under stirring condition and are stirred 2 hours, 2h-8h is stirred under 70 DEG C of -90 DEG C of water bath conditions to viscous Thick shape；
In step 2,4h-24h is dried in 100 DEG C of baking ovens, dried sample is 500 DEG C -700 DEG C in argon gas atmosphere Handle 1h-4h；
In step 3, sample after washing 60 DEG C -100 DEG C dry 4h-24h in vacuum drying oven, obtain porous nitrogen and mix Miscellaneous carbon nanosheet composite negative pole material.
Further, in step 1, the non-ionic polyacrylamide is 1 with Fe(NO3)39H2O mass ratio：(0.3-3) Step.
Further, in step 1, Nickelous nitrate hexahydrate is replaced into Fe(NO3)39H2O, other conditions are identical, and it is more that Ni is made The nitrogen-doped carbon nanosheet composite material in hole.
It is Fe another object of the present invention is to provide a kind of porous nitrogen-doped carbon nanometer sheet composite negative pole material4N/ Fe2O3Nitrogen-doped carbon nano-sheet lithium ion battery negative material porous/Fe.
Another object of the present invention is to provide to prepare the method for lithium battery and include：
Porous nitrogen-doped carbon nanometer sheet composite negative pole material is mixed with 20% conductive agent, then with containing 10% bonding The 1-METHYLPYRROLIDONE solution mixing of agent, is coated on copper foil after stirring, and is put into 100 DEG C of drying in vacuum drying oven；Then Electrode slice is cut out with a diameter of 14mm slicer, is put into 80 DEG C of dry 6~12h in vacuum drying oven；It is then transferred into and is full of argon In the glove box of gas, using metal lithium sheet as to electrode, polypropylene porous film is barrier film, the ethylene carbonate of 1mol/L lithium hexafluoro phosphates Ester and dimethyl carbonate mixed solution are electrolyte, are assembled into button cell.
Further, the mass ratio of the porous nitrogen-doped carbon nanometer sheet composite negative pole material and binding agent is 7：1, it is described Porous nitrogen-doped carbon nanometer sheet composite negative pole material and the mass ratio of conductive agent are 7：2.
Further, the binding agent is Kynoar, and solvent is 1-METHYLPYRROLIDONE, and the conductive agent is conductive carbon It is black.
Advantages of the present invention and good effect are：
Based on discussed above, the present invention provide it is a kind of it is simple, at a low price, the method for green synthesized Fe4N/Fe2O3/ Fe is porous Nitrogen-doped carbon nanosheet composite material, as lithium cell cathode material, it shows preferable stability and high rate performance. Synthesis for the nitride of iron and the application in lithium battery provide new thinking.
Compared with prior art, the present invention has following income effect：
The present invention is by simply stirring, drying, calcining, washing realization, and whole process is fairly simple, and controllability is strong, into This is cheap, is adapted to industrialized production.
Nitride compared to other iron synthesizes, and the nitrogen source that the present invention uses is polyacrylamide, for ammonia, no dirt Dye, it is safe.
It is steady to show excellent circulation in field of lithium ion battery for novel anode material first Application produced by the present invention Qualitative energy and and high rate performance.
Brief description of the drawings
Fig. 1 is the preparation method flow of porous nitrogen-doped carbon nanometer sheet composite negative pole material provided in an embodiment of the present invention Figure.
Fig. 2 is obtained new Fe provided in an embodiment of the present invention4N/Fe2O3Nitrogen-doped carbon nanometer sheet porous/Fe is compound XRD, Raman, N of negative material2Absorption and pore size distribution figure.
In figure：(a) it is XRD；(b) it is Raman figure；(c) it is nitrogen adsorption figure；(d) it is graph of pore diameter distribution.
Fig. 3 is obtained new Fe provided in an embodiment of the present invention4N/Fe2O3Nitrogen-doped carbon nanometer sheet porous/Fe is compound SEM, TEM, HRTEM figure of negative material.
In figure：(a), (b) schemes for SEM；(c), (d) schemes for TEM；(e), (f) schemes for HRTEM.
Fig. 4 is obtained new Fe provided in an embodiment of the present invention4N/Fe2O3Nitrogen-doped carbon nanometer sheet porous/Fe is compound The Mo＆4＆ssbauer spectrum of negative material.
Fig. 5 is obtained new Fe provided in an embodiment of the present invention4N/Fe2O3Nitrogen-doped carbon nanometer sheet porous/Fe is compound The Fe of negative material and bulky grain4N lithium electrical property figure (1C=200mA g-1)。
In figure：(a) it is to be assembled into lithium ion battery with 100mA/g current density, in 3~0.01V voltage range Cycle performance figure；(b) it is high rate performance figure under different current densities；(c) be 1000mA/g current density under cyclicity Can figure.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
Below in conjunction with the accompanying drawings and specific embodiment is further described to the application principle of the present invention.
As shown in figure 1, the preparation side of porous nitrogen-doped carbon nanometer sheet composite negative pole material provided in an embodiment of the present invention Method, comprise the following steps：
S101：1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters, are added under stirring condition 0.75g Fe(NO3)39H2Os are stirred 2 hours, and 4 hours are stirred under 90 DEG C of water bath conditions to thick；
S102：Then dried 6 hours in 100 DEG C of baking ovens, dried sample handles 1 for 700 DEG C in argon gas atmosphere Hour；
S103：Products obtained therefrom deionized water ultrasound and filtering and washing, the sample after washing are done for 70 DEG C in vacuum drying oven It can obtain porous nitrogen-doped carbon nanometer sheet composite negative pole material within dry 10 hours.
Porous nitrogen-doped carbon nanometer sheet composite negative pole material is lithium ion battery negative material.
Nickelous nitrate hexahydrate is replaced into Fe(NO3)39H2O, other conditions are identical, and the porous nitrogen-doped carbons of Ni can be made and receive Rice piece composite.
The condition of the calcining includes：Calcining heat be 500-700 DEG C, calcination time 1-4h, the inert atmosphere by At least one of argon gas, nitrogen and helium provide；
Described water bath condition includes：Bath temperature is 70-90 DEG C, water bath time 2-8h；
Drying condition includes in 100 DEG C of described baking ovens：Drying time is 4-24h；
The non-ionic polyacrylamide is 1 with Fe(NO3)39H2O mass ratio：(0.3-3).
Sample drying condition includes after described washing：Drying temperature is 60-100 DEG C, time 4-24h.
A kind of Fe provided in an embodiment of the present invention4N/Fe2O3Nitrogen-doped carbon nano-sheet lithium ion battery negative pole porous/Fe Material.
Under above-mentioned all conditions, Fe(NO3)39H2O is substituted with Nickelous nitrate hexahydrate, the porous N dopings of Ni can be made Carbon nanosheet composite.
A kind of preparation method of lithium battery provided in an embodiment of the present invention, including：
Another object of the present invention is to provide to prepare the method for lithium battery and include：
Porous nitrogen-doped carbon nanometer sheet composite negative pole material is mixed with 20% conductive agent, then with containing 10% bonding The 1-METHYLPYRROLIDONE solution mixing of agent, is coated on copper foil after stirring, and is put into 100 DEG C of drying in vacuum drying oven；Then Electrode slice is cut out with a diameter of 14mm slicer, is put into 80 DEG C of dry 6~12h in vacuum drying oven；It is then transferred into and is full of argon In the glove box of gas, using metal lithium sheet as to electrode, polypropylene porous film is barrier film, the ethylene carbonate of 1mol/L lithium hexafluoro phosphates Ester and dimethyl carbonate mixed solution are electrolyte, are assembled into button cell.
The mass ratio of the porous nitrogen-doped carbon nanometer sheet composite negative pole material and binding agent is 7：1, it is described porous The mass ratio of nitrogen-doped carbon nanometer sheet composite negative pole material and conductive agent is 7：2.
The binding agent is Kynoar, and solvent is 1-METHYLPYRROLIDONE, and the conductive agent is conductive carbon black.
The material of the present invention is mixed with 20% conductive agent, then it is molten with the 1-METHYLPYRROLIDONE containing 10% binding agent Liquid mixes, and is coated in after stirring on copper foil, is put into 100 DEG C of drying in vacuum drying oven.Then with a diameter of 14mm slicer Electrode slice is cut out, is put into 80 DEG C of dry 6~12h in vacuum drying oven.It is then transferred into the glove box full of argon gas, with lithium metal Piece is to electrode, and polypropylene porous film is barrier film, the ethylene carbonate and dimethyl carbonate (volume ratio of 1mol/L lithium hexafluoro phosphates For 1:1) mixed solution is electrolyte, is assembled into CR2025 button cells, and constant current is carried out on Neware battery test systems and is filled Discharge performance is tested, and discharge and recharge blanking voltage is 0.01~3V.
The application principle of the present invention is further described with reference to specific embodiment.
Embodiment 1
1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters, 0.75g nine is added under stirring condition Nitric hydrate iron stirs 2 hours, 4 hours stir under 90 DEG C of water bath conditions to thick, then drying 6 is small in 100 DEG C of baking ovens When, dried sample 700 degree of 1 hours of processing in argon gas atmosphere, products obtained therefrom deionized water ultrasound and filtering and washing, The 70 DEG C of dryings in vacuum drying oven of sample after washing can obtain the Fe in 10 hours4N/Fe2O3Nitrogen-doped carbon porous/Fe Nanometer sheet composite negative pole material.
Implementation result：By new Fe made from the present embodiment4N/Fe2O3Nitrogen-doped carbon nanometer sheet composite negative pole porous/Fe Material is assembled into battery and carries out charge-discharge test, and Fig. 5 (a) is to be assembled into lithium ion battery with 100mA/g current density, 3 The cycle performance figure of~0.01V voltage range.It can be seen that its first discharge capacity be 995, first reversible capacity be 577mAh/g, first circle coulombic efficiency are 58%, and cyclical stability is preferable.Fig. 5 (b) is the high rate performance under different current densities, Under 2000mA/g current density, still there is a 330mAh/g capacity, high rate performance is fine.Fig. 5 (c) is 1000mA/g electric current Cycle performance figure under density, it can be seen that it still shows good cycle performance under high current density.
Embodiment 2
1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters, 0.375g nine is added under stirring condition Nitric hydrate iron stirs 2 hours, 4 hours stir under 90 DEG C of water bath conditions to thick, then drying 6 is small in 100 DEG C of baking ovens When, dried sample 700 degree of 1 hours of processing in argon gas atmosphere, products obtained therefrom deionized water ultrasound and filtering and washing, The 70 DEG C of dryings in vacuum drying oven of sample after washing can obtain Fe in 10 hours3N/Fe2O3Porous nitrogen-doped carbon nanometer sheet is answered Close negative material.
Implementation result：By new Fe made from the present embodiment3N/Fe2O3Porous nitrogen-doped carbon nanometer sheet composite negative pole material Material is assembled into battery and carries out charge-discharge test, carries out charge-discharge test to it with 100mA/g current density, its appearance of discharging first It is 55% to measure as 832mAh/g, charging capacity 457mAh/g, first charge-discharge coulombic efficiency, and electric discharge is kept after the circle of circulation 100 Capacity is 439mAh/g.
Embodiment 3
1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters, the water of 1.5g nine is added under stirring condition Close ferric nitrate to stir 2 hours, 4 hours stir under 90 DEG C of water bath conditions to thick, then drying 6 hours in 100 DEG C of baking ovens, Dried sample 700 degree of 1 hours of processing in argon gas atmosphere, products obtained therefrom deionized water ultrasound and filtering and washing, water The 70 DEG C of dryings in vacuum drying oven of sample after washing can obtain Fe in 10 hours4N/Fe2O3Nitrogen-doped carbon nanometer sheet porous/Fe Composite negative pole material.
Implementation result：By new Fe made from the present embodiment4N/Fe2O3Nitrogen-doped carbon nanometer sheet composite negative pole porous/Fe Material is assembled into battery and carries out charge-discharge test, carries out charge-discharge test to it with 100mA/g current density, it discharges first Capacity is 886mAh/g, and charging capacity 557mAh/g, first charge-discharge coulombic efficiency is 63%, keeps putting after the circle of circulation 100 Capacitance is 397mAh/g.
Embodiment 4
1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters, 0.75g six is added under stirring condition Nitric hydrate nickel stirs 2 hours, 4 hours stir under 90 DEG C of water bath conditions to thick, then drying 6 is small in 100 DEG C of baking ovens When, dried sample 700 degree of 1 hours of processing in argon gas atmosphere, products obtained therefrom deionized water ultrasound and filtering and washing, It is compound that the 70 DEG C of dryings in vacuum drying oven of sample after washing can obtain the porous nitrogen-doped carbon nanometer sheets of the Ni in 10 hours Material.
Embodiment 5
1.5g non-ionic polyacrylamides are weighed, are dissolved in 150mL deionized waters, 0.75g nine is added under stirring condition Nitric hydrate iron stirs 2 hours, 4 hours stir under 90 DEG C of water bath conditions to thick, then drying 6 is small in 100 DEG C of baking ovens When, dried sample 700 degree of 1 hours of processing in argon gas atmosphere, products obtained therefrom deionized water ultrasound and filtering and washing, The 70 DEG C of dryings in vacuum drying oven of sample after washing can obtain the Fe in 10 hours4N/Fe2O3Nitrogen-doped carbon porous/Fe Nanometer sheet composite negative pole material.
Embodiment 6
1.5g non-ionic polyacrylamides are weighed, are dissolved in 200mL deionized waters, 0.75g nine is added under stirring condition Nitric hydrate iron stirs 2 hours, 4 hours stir under 90 DEG C of water bath conditions to thick, then drying 6 is small in 100 DEG C of baking ovens When, dried sample 700 degree of 1 hours of processing in argon gas atmosphere, products obtained therefrom deionized water ultrasound and filtering and washing, The 70 DEG C of dryings in vacuum drying oven of sample after washing can obtain the Fe in 10 hours4N/Fe2O3Nitrogen-doped carbon porous/Fe Nanometer sheet composite negative pole material.
Embodiment 7
1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters, 0.75g nine is added under stirring condition Nitric hydrate iron stirs 2 hours, 4 hours stir under 70 DEG C of water bath conditions to thick, then drying 6 is small in 100 DEG C of baking ovens When, dried sample 700 degree of 1 hours of processing in argon gas atmosphere, products obtained therefrom deionized water ultrasound and filtering and washing, The 70 DEG C of dryings in vacuum drying oven of sample after washing can obtain the Fe in 10 hours4N/Fe2O3Nitrogen-doped carbon porous/Fe Nanometer sheet composite negative pole material.
Embodiment 8
1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters, 0.75g nine is added under stirring condition Nitric hydrate iron stirs 2 hours, 4 hours stir under 80 DEG C of water bath conditions to thick, then drying 6 is small in 100 DEG C of baking ovens When, dried sample 700 degree of 1 hours of processing in argon gas atmosphere, products obtained therefrom deionized water ultrasound and filtering and washing, The 70 DEG C of dryings in vacuum drying oven of sample after washing can obtain the Fe in 10 hours4N/Fe2O3Nitrogen-doped carbon porous/Fe Nanometer sheet composite negative pole material.
Embodiment 9
1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters, 0.75g nine is added under stirring condition Nitric hydrate iron stirs 2 hours, 4 hours stir under 80 DEG C of water bath conditions to thick, then drying 6 is small in 100 DEG C of baking ovens When, dried sample 500 degree of 1 hours of processing in argon gas atmosphere, products obtained therefrom deionized water ultrasound and filtering and washing, The 70 DEG C of dryings in vacuum drying oven of sample after washing can obtain the Fe in 10 hours4N/Fe2O3Nitrogen-doped carbon porous/Fe Nanometer sheet composite negative pole material.
Embodiment 9
1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters, 0.75g nine is added under stirring condition Nitric hydrate iron stirs 2 hours, 4 hours stir under 80 DEG C of water bath conditions to thick, then drying 6 is small in 100 DEG C of baking ovens When, dried sample 500 degree of 1 hours of processing in argon gas atmosphere, products obtained therefrom deionized water ultrasound and filtering and washing, The 70 DEG C of dryings in vacuum drying oven of sample after washing can obtain the Fe in 10 hours4N/Fe2O3Nitrogen-doped carbon porous/Fe Nanometer sheet composite negative pole material.
Embodiment 10
1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters, 0.75g nine is added under stirring condition Nitric hydrate iron stirs 2 hours, 4 hours stir under 80 DEG C of water bath conditions to thick, then drying 6 is small in 100 DEG C of baking ovens When, dried sample 600 degree of 1 hours of processing in argon gas atmosphere, products obtained therefrom deionized water ultrasound and filtering and washing, The 70 DEG C of dryings in vacuum drying oven of sample after washing can obtain the Fe in 10 hours4N/Fe2O3Nitrogen-doped carbon porous/Fe Nanometer sheet composite negative pole material.
Fig. 2 is obtained new Fe provided in an embodiment of the present invention4N/Fe2O3Nitrogen-doped carbon nanometer sheet porous/Fe is compound XRD, Raman, N of negative material2Absorption and pore size distribution figure.
In figure：(a) it is XRD；(b) it is Raman figure；(c) it is nitrogen adsorption figure；(d) it is graph of pore diameter distribution.
Fig. 3 is obtained new Fe provided in an embodiment of the present invention4N/Fe2O3Nitrogen-doped carbon nanometer sheet porous/Fe is compound SEM, TEM, HRTEM figure of negative material.
In figure：(a), (b) schemes for SEM；(c), (d) schemes for TEM；(e), (f) schemes for HRTEM.
Fig. 4 is obtained new Fe provided in an embodiment of the present invention4N/Fe2O3Nitrogen-doped carbon nanometer sheet porous/Fe is compound The Mo＆4＆ssbauer spectrum of negative material.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.

Claims (8)

  1. A kind of 1. preparation method of porous nitrogen-doped carbon nanometer sheet composite negative pole material, it is characterised in that the porous nitrogen The preparation method of doping carbon nanosheet composite negative pole material includes：
    Step 1, non-ionic polyacrylamide is dissolved in deionized water, Fe(NO3)39H2O is added under stirring condition and is stirred Mix, stirred under 90 DEG C of water bath conditions to thick；
    Step 2, then dry in an oven, dried sample is handled in argon gas atmosphere；
    Step 3, products obtained therefrom deionized water ultrasound and filtering and washing, the sample after washing are dried in vacuum drying oven, obtained Porous nitrogen-doped carbon nanometer sheet composite negative pole material.
  2. 2. the preparation method of porous nitrogen-doped carbon nanometer sheet composite negative pole material as claimed in claim 1, it is characterised in that In step 1, specifically include：1.5g non-ionic polyacrylamides are weighed, are dissolved in 100mL deionized waters, are added under stirring condition Enter 0.75g Fe(NO3)39H2Os to stir 2 hours, 2h-8h is stirred under 70 DEG C of -90 DEG C of water bath conditions to thick；
    In step 2,4h-24h, 500 DEG C of -700 DEG C of processing in argon gas atmosphere of dried sample are dried in 100 DEG C of baking ovens 1h-4h；
    In step 3, sample after washing 60 DEG C -100 DEG C dry 4h-24h in vacuum drying oven, porous nitrogen-doped carbon is obtained Nanometer sheet composite negative pole material.
  3. 3. the preparation method of porous nitrogen-doped carbon nanometer sheet composite negative pole material as claimed in claim 1, it is characterised in that In step 1, the non-ionic polyacrylamide is 1 with Fe(NO3)39H2O mass ratio：(0.3-3) step.
  4. 4. the preparation method of porous nitrogen-doped carbon nanometer sheet composite negative pole material as claimed in claim 1,
    In step 1, Nickelous nitrate hexahydrate is replaced into Fe(NO3)39H2O, other conditions are identical, and the porous nitrogen-doped carbons of Ni are made Nanosheet composite material.
  5. 5. a kind of preparation method of porous nitrogen-doped carbon nanometer sheet composite negative pole material as claimed in claim 1 prepares more The nitrogen-doped carbon nanometer sheet composite negative pole material in hole, it is characterised in that the porous nitrogen-doped carbon nanometer sheet composite negative pole material Expect for Fe4N/Fe2O3Nitrogen-doped carbon nano-sheet lithium ion battery negative material porous/Fe.
  6. 6. a kind of method for preparing lithium battery using nitrogen-doped carbon nanometer sheet composite negative pole material porous described in claim 5, Characterized in that, the method for preparing lithium battery includes：
    Porous nitrogen-doped carbon nanometer sheet composite negative pole material is mixed with 20% conductive agent, then with containing 10% binding agent 1-METHYLPYRROLIDONE solution mixes, and is coated in after stirring on copper foil, is put into 100 DEG C of drying in vacuum drying oven；Then with straight Footpath is that 14mm slicer cuts out electrode slice, is put into 80 DEG C of dry 6~12h in vacuum drying oven；It is then transferred into full of argon gas In glove box, using metal lithium sheet as to electrode, polypropylene porous film is barrier film, the ethylene carbonate of 1mol/L lithium hexafluoro phosphates and Dimethyl carbonate mixed solution is electrolyte, is assembled into button cell.
  7. 7. the method for preparing lithium battery as claimed in claim 6, it is characterised in that the porous nitrogen-doped carbon nanometer sheet is compound The mass ratio of negative material and binding agent is 7：1, the porous nitrogen-doped carbon nanometer sheet composite negative pole material and conductive agent Mass ratio is 7：2.
  8. 8. the method for preparing lithium battery as claimed in claim 6, it is characterised in that the binding agent is Kynoar, solvent For 1-METHYLPYRROLIDONE, the conductive agent is conductive carbon black.
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CN113066953A (en) * 2021-04-26 2021-07-02 肇庆市华师大光电产业研究院 Preparation method of lithium-sulfur battery positive electrode heterojunction material
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CN113066953B (en) * 2021-04-26 2022-04-05 肇庆市华师大光电产业研究院 Preparation method of lithium-sulfur battery positive electrode heterojunction material
CN113371688A (en) * 2021-06-07 2021-09-10 南阳师范学院 Preparation method of novel iron nitride and porous carbon composite anode material
CN116093297A (en) * 2023-03-29 2023-05-09 南阳师范学院 Preparation method of carbon-coated ferronitride and nitrogen-doped porous carbon nano-sheet composite anode material

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