CN107170994A - A kind of Fe N doping porous carbon oxygen reduction catalyst - Google Patents

A kind of Fe N doping porous carbon oxygen reduction catalyst Download PDF

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Publication number
CN107170994A
CN107170994A CN201710245791.8A CN201710245791A CN107170994A CN 107170994 A CN107170994 A CN 107170994A CN 201710245791 A CN201710245791 A CN 201710245791A CN 107170994 A CN107170994 A CN 107170994A
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oxygen reduction
porous carbon
carbon oxygen
solution
reduction catalyst
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林雨青
李长青
何传生
孙凤展
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Capital Normal University
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Capital Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

Adulterated porous carbon oxygen reduction catalyst the present invention relates to a kind of Fe N, Fe N doping porous carbon oxygen reduction catalyst is prepared by the following method, lyophilized after iron ion uniformly mix with silk fibroin protein solution, then to freezing after the processing of product high temperature cabonization.The present invention is environmentally friendly, cheap with nature Green, it is easy to which widely available silk cocoon successfully synthesizes the effective catalyst Fe N doping porous carbons for oxygen reduction for precursor.Pass through the optimization to preparation technology, it is determined that suitable reaction condition, made catalyst possesses plurality of advantages, such as, with larger current density, higher electron transfer number, relatively low hydrogen peroxide yield, good stability and methanol tolerance poisons ability.

Description

A kind of Fe-N doping porous carbon oxygen reduction catalyst
Technical field
The present invention relates to catalyst field, and in particular to a kind of redox electrocatalysis material with loose structure.
Background technology
The energy is developing national economy and the important substance basis uplifted the people's living standard, and is also to directly affect economic hair One key factor of exhibition.Since 21 century, shortage of resources that traditional energy utilization patterns are brought, environmental pollution and The problems such as greenhouse effects, is more prominent, therefore traditional energy resource structure and its Land use systems are increasingly difficult in adapt to human survival hair The need for exhibition.In recent years, metal-air battery was by scientific and technological circle and industrial circle extensive concern, and industrialization prospect is very bright and clear.Make For a kind of new fuel cell, metal-air battery is that a kind of fuel that will be present in directly is converted with the chemical energy in oxidant For the TRT of electric energy.It is widely used to automobile at present, space shuttle is submarine, underwater robot, communication system, medium and small Scale power station, domestic power supply, and with high efficiency, short pollution-free, construction period, easy care and the low feature of cost.At present, It is not yet to develop high-performance, low cost and meet commercialization to require to limit one of main factor of metal-air battery motorization Oxygen reduction catalyst.
Noble metal is one of active highest oxygen reduction catalyst for being found so far.However, noble metal catalyst More prominent shortcoming is expensive, shortage of resources, in the electrolytic solution easily reunion and corrosion.Which greatly limits It limits the fast development of fuel cell industries in the application of fuel cell.
At present, two major class hydrogen reduction non-noble catalyst mainly are developed：One class is the transition gold enriched containing the earth's crust Belong to the carbon-based material of (Fe or/and Co), the carbon material of another kind of hetero atom (such as B, N, S, the P) doping for being free from metal.Wherein The carbon material of N doping containing metal, due to high electro catalytic activity, long-time stability, environment friendly and low cost And widely studied.Wherein Wu etc. is with the aerogel carried Fe of nitrogen-doped graphene3O4Nano particle is prepared for a kind of three-dimensional Fe3O4/ NGA non-precious metal catalysts, with preferable hydrogen reduction performance and durability, the three-dimensional porous structure of aeroge formation Higher specific surface area for improve oxygen reduction reaction catalytic performance play an important roll (J.Am.Chem.Soc., 2012, 134(22):9082).Liu etc. reports a kind of Fe/NG/C composites with three-dimensional structure, and wherein carbon black is tied as support The interlayer that structure is located at graphene-structured prevents the stacking of graphene-structured, so as to ensure O2Graphene layer surface can be transported Catalytic active site participate in oxygen reduction reaction (ElectrochimicaActa, 2012,81:313).Thus, in porous carbon materials It is middle to introduce inexpensive metal, fabulous catalytic activity can be not only obtained, cost can also be substantially reduced, large-scale industry is realized Change application.
The content of the invention
It is an object of the invention to provide a kind of Fe-N doping porous carbon oxygen reduction catalysts, the Fe-N doping porous carbon oxygen Reducing catalyst is prepared by the following method, after iron ion is uniformly mixed with silk fibroin protein solution, is freezed, then to after lyophilized Product carry out high temperature cabonization processing.Catalyst of the present invention is during preparation, before high-temperature process, need to be by fibroin Protein solution is freeze-dried, to maintain original chemical composition and physical property (such as loose structure, colloidal nature), During Pintsch process, the decomposition of internal organic matter can form loose structure and the passage being mutually communicated, beneficial to electronics in catalytic process With the transfer of material.
It is preferred that, the mass ratio of fibroin albumen is 1 in the iron ion and the silk fibroin protein solution：(3.3~4.3). Silk fibroin protein solution is obtained by mass ratio doping, more holes and the duct interpenetrated can be obtained after freezing, it is beneficial The formation of catalyst loose structure when in Pintsch process, lifts the overall performance of catalyst.
It is preferred that, it is characterised in that the concentration of fibroin albumen is 3.5wt%~4.5wt% in the silk fibroin protein solution. Using the fibroin albumen of above-mentioned concentration, mutually overlapped between albumen after freezing, matter is soft relatively light, with fluffy structure, is conducive to With the further complexing of iron ion.
It is preferred that, the temperature of the high temperature cabonization processing is 700~900 DEG C, and the time is 2~4h；Under the conditions of this kind, processing Obtained catalyst carbonizing degree is high, and good conductivity is conducive to electro transfer, in high-temperature process, and internal organic matter also can Decompose, form loose structure, beneficial to the absorption of oxygen, promote the progress of electrocatalytic reaction.
Further preferably, the temperature of the high temperature cabonization processing is 790~810 DEG C；Optimal is 800 DEG C.
It is preferred that, heating rate is 2~4 DEG C/min during heating；Nitrogen is passed through during heating and carbonization treatment Gas or inert gas are protected.
It is further preferred that catalyst of the present invention, its preparation method comprises the following steps：
1) compound concentration is 3.5wt%~4.5wt% silk fibroin protein solution, by iron ion and the mass ratio of fibroin albumen For 1：(3.3~4.3) iron ion is added, the two is well mixed, homogeneous phase solution is formed；
2) above-mentioned homogeneous phase solution is subjected to frozen dried under conditions of -40 DEG C~-35 DEG C；
3) product of gained after frozen dried is pressed to 2~4 DEG C/min speed liter under the protection of nitrogen or inert gas Temperature is to 790~810 DEG C, and 2~2.5h of carbonization treatment, obtains Fe-N doping porous carbon oxygen reduction catalysts at this temperature.
Above-mentioned preferred scheme, the best results when the temperature of carbonization treatment is 800 DEG C.
Most preferably, catalyst of the present invention, its preparation method comprises the following steps：
1) compound concentration is 4% silk fibroin protein solution, is 1 by the mass ratio of iron ion and fibroin albumen：3.87 add Iron ion, the two is well mixed, and forms homogeneous phase solution；
2) above-mentioned homogeneous phase solution is subjected to frozen dried under conditions of -40 DEG C~-35 DEG C；
3) product of gained after frozen dried is pressed to 2~4 DEG C/min speed liter under the protection of nitrogen or inert gas Temperature is to 800 DEG C, and carbonization treatment 2h, obtains Fe-N doping porous carbon oxygen reduction catalysts at this temperature.
Fibroin albumen of the present invention can directly be bought or laboratory is prepared；
It is preferred that, the preparation method of the silk fibroin protein solution comprises the following steps：
1) by the silk cocoon shredded according to bath raio 1:80-1:120 are placed in Na2CO3In the aqueous solution, heating refining 2 times；Will refining Silk cocoon afterwards is fully cleaned with distilled water, is spontaneously dried, is obtained fibroin fiber；
2) by the fibroin fiber according to bath raio 1:20-1:30 are placed in CaCl2Heated in water solution dissolves, and obtains fibroin albumen Thick solution；
3) the thick solution of the fibroin albumen is placed in cellulose dialysis film after dialysis purification, obtains fibrin solution.
Further preferably, used Na during the heating refining2CO3Aqueous solution mass fraction be 0.4~ 0.6wt%, 95-100 DEG C of refining temperature, refining time is each 20-40min；
And/or the step 2) used in CaCl2Aqueous solution mass fraction is 48~52wt%, and solution temperature is 95-100 DEG C, the time is 10-30min.
And/or the step 3) in the molecular components of cellulose dialysis film that use be 12000-14000.
It is another object of the present invention to protect Fe-N doping porous carbon oxygen reduction catalysts of the present invention to be gone back in oxidation Application in former electro-catalysis.
Final object of the present invention is metal air fuel cell of the protection containing material of the present invention；It is preferred that , the metal air fuel cell is alkaline fuel cell, and the negative electrode of fuel cell contains the Fe-N doped porous carbons Material.
Catalyst of the present invention has the advantages that：
1) present invention is environmentally friendly, cheap with nature Green, it is easy to which widely available silk cocoon is that precursor is successfully synthesized It is used for C sources, N sources in the effective catalyst Fe-N doping porous carbons of oxygen reduction, this catalyst green all from silk cocoon Colour circle protect, it is cheap.And this catalyst contains the macropore of three-dimensional communication.
2) Fe-N doping porous carbon oxygen reduction catalyst of the present invention, the carrying current that catalytic oxidation-reduction reaction is obtained Density highest can reach 5.53mA cm-2, better than commercial Pt/C (4.15mA cm-2)。
3) Fe-N doping porous carbon oxygen reduction catalyst of the present invention, average electron transfer number n is 3.88 to the maximum, with Commercial Pt/C (n=3.95) quite, hydrogen peroxide yield<12.3% (vs.RHE 0-0.9V).
4) Fe-N doping porous carbon oxygen reduction catalyst of the present invention, catalytic oxidation-reduction course of reaction stability is good, Only occur the oxidation reaction of part methanol, therefore with preferable methanol tolerance performance, be much better than the Pt/C of commercialization.
Brief description of the drawings
Fig. 1 is SEM and the TEM contrast of the porous carbon materials of gained in the embodiment of the present invention 1 and contrast material N-C-800 Figure.Wherein a, b are respectively comparative example N-C-800, and embodiment 1Fe-N-C-800 SEM figures；C, d are respectively N-C-800, Fe- N-C-800 TEM figures.
Fig. 2 shows the embodiment of the present invention 1, and embodiment 2, circulation of the embodiment 3 to oxygen reduction lies prostrate the ratio of (CV) curve Relatively scheme.
Fig. 3 is LSV (linear scan curve) contrasts of embodiment 1,2,3 and N-C-800 and the 20%Pt-C materials of business Figure.
Fig. 4 is Fe-N-C-800 in embodiment 1, and ability comparison diagram is poisoned with the 20%Pt-C methanol tolerances of business.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
The present embodiment is related to a kind of Fe-N doping porous carbon oxygen reduction catalyst, prepares by the following method：
1st, the preparation of fibroin albumen
1) 2g Na accurately are weighed2CO3, it is dissolved in 400mL distilled water, by Na2CO3Solution is heated to 98 DEG C, places into The silk cocoon refining that 4g is shredded, refines 30min, refining is twice every time；Cocoon layer after refining is fully cleaned with distilled water, done naturally It is dry, obtain fibroin fiber.
2) 50g CaCl are weighed2Solid is dissolved in 100mL distilled water, is heated to 98 DEG C, adds step 2) in it is dried Fibroin fiber, heats 10min, obtains the translucent thick thick solution of shape fibroin albumen.
3) by step 3) obtained thick shape solution poured into the cellulose dialysis film that molecular components are 12000-14000, and Dialyse 3d in flowing water, obtains silk fibroin protein solution, the concentration of wherein fibroin albumen is about 4wt%；
2nd, the preparation of Fe-N doping porous carbon oxygen reduction catalyst
1) taking above-mentioned silk fibroin protein solution 60g to be placed in 100mL beakers, (mass fraction of wherein fibroin albumen is 4wt%), 3g iron chloride crystal is added, and is stirred in magnetic stirring apparatus, homogeneous phase solution (iron ion and fibroin egg is formed White mass ratio is 1：3.87).
2) it is placed in freeze dryer, is freezed at -35 DEG C after the homogeneous phase solution is freezed completely, forms yellowish-brown lightweight many PFP foam；
3) the filemot protein foam is placed in the heating of tube furnace high temperature (2.5 DEG C/min of heating rate, heating temperature Spend for 800 DEG C, and maintain two hours, and then obtain dark brown jelly, be Fe-N-C-800.High-temperature heating and the mistake of heating Cheng Zhong, tube furnace keeps being passed through nitrogen.
The SEM (ESEM) and TEM (transmission electron microscope) image of Fe-N-C-800 made from the present embodiment is as shown in Figure 1； CV (cyclic voltammetric) is as shown in Figure 2；LSV (linear scan) and business 20%Pt-C contrasts are as shown in Figure 3；Methanol tolerance poisons ability (i-t) such as Fig. 4.
Embodiment 2
Experimental procedure is same as Example 1, during difference is high-temperature heating treatment, the heating in control tube furnace Temperature is 700 DEG C, is prepared into identical, electrochemical test method in Fe-N-C-700, characterizing method (SEM, TEM) be the same as Example 1 (CV, LSV, i-t) also be the same as Example 1.
Embodiment 3
Experimental procedure is same as Example 1, during difference is high-temperature heating treatment, the heating in control tube furnace Temperature is 900 DEG C, is prepared into identical, electrochemical test method in Fe-N-C-900, characterizing method (SEM, TEM) be the same as Example 1 (CV, LSV, i-t) is also same as Example 1.
Comparative example
Compared with Example 1, its difference is, in step 2, omits step 1), that is, omit addition iron chloride crystal Operation, only prepares catalyst by fibroin albumen.
Interpretation of result
Fig. 1 shows the pattern of the N-C-800 products in embodiment 1 and comparative example.Visible embodiment is wherein schemed by SEM 1 catalyst that Fe-N doping is made has loose structure, and TEM is schemed after visible ferro element incorporation, it is suppressed that the reunion of fibroin albumen, Internally generate more defects simultaneously.
Fig. 2 is shown mixes iron char-forming material containing saturation N under three kinds of different temperatures2And O20.1mol/L hydroxides Cyclic voltammetry curve in potassium solution, wherein Fe-N-C-800 compare Fe-N-C-700, and Fe-N-C-900 has the oxygen of corrigendum also Former current potential (0.84V vs RHE).
Fig. 3 shows linear scan curve of five kinds of materials in 0.1mol/L potassium hydroxide solutions, wherein Fe-N-C- 800 starting point position is 0.94V vs RHE, and with commercial pallium-on-carbon close to (0.98V vs RHE), and limiting current density is 5.53mA cm-2, better than commercial pallium-on-carbon (4.15mA cm-2), the test condition of five kinds of materials is identical.
The result of above electrochemical test shows, in material Fe-N-C-800 compared to Fe-N-C-700, N-C-800 and Fe-N-C-900 has most positive take-off potential, maximum electron transfer number, and maximum current density, i.e. Fe-N-C-800 tools There is best electro-catalysis effect.
The experiment that methanol tolerance poisons ability is：In alkaline oxygen saturated solution, 1mol/L methanol is added, is tested respectively Fe-N-C-800 catalyst and 20% pallium-on-carbon electric current of business change with time.
Fig. 4 ordinates % represents to add after methanol, and contrast material and catalyst start the ratio of electric current.It, which embodies, adds first The change of catalytic current after alcohol, changes smaller explanation catalyst catalytic performance better, it is seen that the catalysis of Fe-N-C-800 catalyst Better performances.
Although above having made to retouch in detail to the present invention with general explanation, embodiment and experiment State, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art 's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, are belonged to claimed Scope.

Claims (10)

  1. A kind of porous carbon oxygen reduction catalyst 1. Fe-N adulterates, it is characterised in that the Fe-N doping porous carbons hydrogen reduction catalysis Agent is prepared by the following method, and iron ion is uniformly mixed with silk fibroin protein solution, is freezed, and then the product after lyophilized is carried out High temperature cabonization processing.
  2. The porous carbon oxygen reduction catalyst 2. Fe-N according to claim 1 adulterates, it is characterised in that the iron ion and institute The mass ratio for stating fibroin albumen in silk fibroin protein solution is 1：(3.3~4.3).
  3. The porous carbon oxygen reduction catalyst 3. Fe-N according to claim 2 adulterates, it is characterised in that the fibroin albumen is molten The concentration of fibroin albumen is 3.5wt%~4.5wt% in liquid.
  4. 4. the Fe-N doping porous carbon oxygen reduction catalysts according to any one of claims 1 to 3, it is characterised in that described The temperature of high temperature cabonization processing is 700~900 DEG C, and the time is 2~4h；It is preferred that 790~810 DEG C.
  5. The porous carbon oxygen reduction catalyst 5. Fe-N according to claim 4 adulterates, it is characterised in that heated up in temperature-rise period Speed is 2~4 DEG C/min；Nitrogen is passed through during heating and carbonization treatment or other inert gases are protected.
  6. 6. the Fe-N doping porous carbon oxygen reduction catalysts according to any one of Claims 1 to 5, it is characterised in that it is made Preparation Method comprises the following steps：
    1) compound concentration is 3.5wt%~4.5wt% silk fibroin protein solution, is 1 by the mass ratio of iron ion and fibroin albumen： (3.3~4.3) iron ion is added, the two is well mixed, homogeneous phase solution is formed；
    2) above-mentioned homogeneous phase solution is subjected to frozen dried under conditions of -40 DEG C~-35 DEG C；
    3) product of gained after frozen dried is pressed to 2~4 DEG C/min speed liter under the protection of nitrogen or other inert gases Temperature is to 790~810 DEG C, and 2~2.5h of carbonization treatment, obtains Fe-N doping porous carbon oxygen reduction catalysts at this temperature.
  7. 7. the Fe-N doping porous carbon oxygen reduction catalysts according to claim 1 or 6, it is characterised in that the fibroin egg The preparation method of white solution comprises the following steps：
    1) by the silk cocoon shredded according to bath raio 1:80-1:120 are placed in Na2CO3In the aqueous solution, heating refining 2 times；After refining Silk cocoon is fully cleaned with distilled water, is spontaneously dried, is obtained fibroin fiber；
    2) by the fibroin fiber according to bath raio 1:20-1:30 are placed in CaCl2Heated in water solution dissolves, and obtains fibroin albumen slightly molten Liquid；
    3) the thick solution of the fibroin albumen is placed in cellulose dialysis film after dialysis purification, obtains fibrin solution.
  8. The porous carbon oxygen reduction catalyst 8. Fe-N according to claim 7 adulterates, it is characterised in that the heating refining During used in Na2CO3Aqueous solution mass fraction is 0.4~0.6wt%, and 95-100 DEG C of refining temperature, refining time is every Secondary 20-40min；
    And/or the step 2) used in CaCl2Aqueous solution mass fraction is 48~52wt%, and solution temperature is 95-100 DEG C, the time is 10-30min；
    And/or the step 3) in the molecular components of cellulose dialysis film that use be 12000-14000.
  9. 9. the Fe-N described in any one of claim 1~8 adulterates porous carbon oxygen reduction catalyst in redox electro-catalysis Using.
  10. 10. include the metal air fuel electricity of any one of the claim 1~8 Fe-N doping porous carbon oxygen reduction catalyst Pond；It is preferred that, the metal air fuel cell is alkaline fuel cell, and it is many that the negative electrode of fuel cell contains the Fe-N doping Hole carbon material.
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CN108470916A (en) * 2018-02-07 2018-08-31 深圳大学 It is a kind of using three-dimensional porous carbon material as the fuel cell oxygen reduction catalyst of raw material and preparation method
CN108855179A (en) * 2018-05-25 2018-11-23 青岛大学 Animal blood saltout thermal polymerization preparation auto-dope Fe-N-C oxygen reduction electro-catalyst method
CN109622014A (en) * 2018-12-12 2019-04-16 安徽大学 A kind of preparation method of the catalyst of electro-catalysis oxygen generation hydrogen peroxide
CN110371970A (en) * 2019-08-12 2019-10-25 四川轻化工大学 A kind of preparation method of the rich nitrogen grading porous carbon material of high-specific surface area
CN111715256A (en) * 2020-06-10 2020-09-29 江苏大学 Preparation method of silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles
CN111977648A (en) * 2020-08-19 2020-11-24 苏州大学 Silk fibroin source nitrogen-doped porous carbon material and preparation method thereof
CN112018358A (en) * 2020-08-17 2020-12-01 五邑大学 Nitrogen-doped/carbon-coated potassium titanate material and preparation method thereof
CN114373921A (en) * 2021-12-27 2022-04-19 合肥国轩高科动力能源有限公司 Modified ternary cathode material, preparation method thereof and lithium ion battery

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CN106252673A (en) * 2016-08-22 2016-12-21 首都师范大学 A kind of preparation method of Fe N/C oxygen reduction reaction catalyst based on natural plants tissue

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108470916A (en) * 2018-02-07 2018-08-31 深圳大学 It is a kind of using three-dimensional porous carbon material as the fuel cell oxygen reduction catalyst of raw material and preparation method
CN108470916B (en) * 2018-02-07 2020-09-01 深圳大学 Fuel cell oxygen reduction catalyst taking three-dimensional porous carbon material as raw material and preparation method thereof
CN108855179A (en) * 2018-05-25 2018-11-23 青岛大学 Animal blood saltout thermal polymerization preparation auto-dope Fe-N-C oxygen reduction electro-catalyst method
CN109622014A (en) * 2018-12-12 2019-04-16 安徽大学 A kind of preparation method of the catalyst of electro-catalysis oxygen generation hydrogen peroxide
CN110371970A (en) * 2019-08-12 2019-10-25 四川轻化工大学 A kind of preparation method of the rich nitrogen grading porous carbon material of high-specific surface area
CN111715256A (en) * 2020-06-10 2020-09-29 江苏大学 Preparation method of silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles
CN111715256B (en) * 2020-06-10 2023-04-18 江苏大学 Preparation method of silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles
CN112018358A (en) * 2020-08-17 2020-12-01 五邑大学 Nitrogen-doped/carbon-coated potassium titanate material and preparation method thereof
CN111977648A (en) * 2020-08-19 2020-11-24 苏州大学 Silk fibroin source nitrogen-doped porous carbon material and preparation method thereof
CN114373921A (en) * 2021-12-27 2022-04-19 合肥国轩高科动力能源有限公司 Modified ternary cathode material, preparation method thereof and lithium ion battery
CN114373921B (en) * 2021-12-27 2023-03-10 合肥国轩高科动力能源有限公司 Modified ternary cathode material, preparation method thereof and lithium ion battery

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Application publication date: 20170915