CN105762362A - Carbon-coated ferroferric oxide/nitrogen-doped grapheme composite material and preparation method thereof - Google Patents
Carbon-coated ferroferric oxide/nitrogen-doped grapheme composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a composite material and a preparation method thereof, in particular to a carbon-coated ferroferric oxide/nitrogen-doped grapheme composite material and a preparation method thereof, and belongs to the technical fields of material and electrochemistry. The composite material comprises carbon-coated ferroferric oxide and nitrogen-doped grapheme, and in the composite material, ferroferric oxide is uniformly distributed on the surface of a grapheme sheet layer. The composite material comprises carbon-coated ferroferric oxide and nitrogen-doped grapheme, and has excellent cycling performance and rate capability during use as a lithium ion battery cathode material. In addition, the composite material can effectively buffer the volume effect of ferroferric oxide in electrochemical reaction, meanwhile further improves the electrical conductivity, and greatly reduces the impedance of a battery, thereby effectively improving the electrochemical performance.
Description
Technical field
The present invention relates to a kind of composite and preparation method thereof, it is specifically related to a kind of carbon coated ferriferrous oxide/N doping graphite composite material and preparation method thereof, belong to material and technical field of electrochemistry, the invention still further relates to the application in lithium ion battery negative material of this composite.
Background technology
Along with the exhaustion of petroleum resources, promote that the development of regenerative resource has great Social and economic [email protected] the energy storage new technique being application background with chemical energy storage, lithium ion has open-circuit voltage height, has extended cycle life, energy density height, memory-less effect, the advantage such as environmentally friendly, the superior electrical property can not compared with other secondary cells (Ni-MH battery, lead-acid battery, nickel-cadmium cell) and external form is variable etc. that advantage has captured rapidly numerous market segment, become the first-selection of various portable type electronic product, and to the new energy field such as big-and-middle-sized energy storage device and photovoltaic engineering extensions such as electric automobiles.At present commercial lithium ion battery mainly adopts graphite cathode, and the theoretical capacity (372mAhg that graphite cathode is relatively low-1) significantly limit the lifting of battery whole volume, therefore in the urgent need to developing the lithium ion battery negative material of new high power capacity.Recent study shows, transition metal oxide is hopeful to replace conventional graphite negative pole to become a new generation's high-capacity cathode material most.
In transition metal oxide, ferroso-ferric oxide abundance, environmental friendliness, and there is high theoretical capacity (924mAhg-1), become the focus of research.But, ferriferrous oxide material electrical conductivity is relatively low, and there is bigger change in volume in the embedding de-process of lithium ion, causes the inefficacy of material, significantly limits its application.
Carbon cladding can improve Fe3O4Chemical property, people have employed a lot of method and it be modified, for instance prepares the Fe of nanorize3O4, carbon cladding nanometer Fe3O4And nano level Fe3O4/ C composite etc..In lithium ion charge and discharge process, nano material is owing to having bigger specific surface area, shorter the evolving path and diffusion rate faster, it is possible to absorbs and stores substantial amounts of lithium ion, being conducive to improving its chemical property；Carbon coating layer can stop active substance that bigger change in volume occurs in battery charge and discharge process, and avoids the reunion of active substance；It is high that carbon base body also has good electric conductivity, lithium permeability, and the feature such as stable electrochemical property.
At present, carbon cladding Fe3O4The preparation method of nano composite material mainly has hydro-thermal method, thermal decomposition method etc..Chinese patent if publication number is CN102790217B the invention discloses a kind of carbon coated ferriferrous oxide lithium ion battery cathode material and its preparation method；This negative material is carbon cladding Fe3O4Composite, its particle diameter is between 1～100nm；Its preparation process: adopt NaCl as dispersant and carrier, it is sufficiently mixed with metal oxide source and solid carbon source；By mixed solution vacuum drying, obtain mixture；Mixture is put in tube furnace and calcines under an inert atmosphere, obtain calcined product；Calcined product is washed, grinds and obtain carbon-clad metal oxide nano particles.And for example publication number is that the patent application of CN103647041A discloses a kind of carbon coated ferriferrous oxide nano wire and preparation method thereof and its application in preparing lithium ion battery；The Chinese patent application that publication number is CN104993126A discloses a kind of carbon cladding Fe3O4Nano-particle lithium ion battery negative material preparation method and application thereof.Visible, in prior art, the research of the overwhelming majority focuses mostly on and is coated with Fe at carbon3O4In the preparation method of nano composite material.
Summary of the invention
It is an object of the invention to provide a kind of composite, this material is made up of carbon coated ferriferrous oxide and nitrogen-doped graphene composite, and this composite is as, in lithium ion battery negative material use procedure, having circulation and the high rate performance of excellence.
Technical scheme:
First technical problem that the invention solves the problems that is to provide a kind of composite, and described composite is made up of carbon coated ferriferrous oxide and nitrogen-doped graphene, and in described composite, ferroso-ferric oxide is evenly distributed in the surface of graphene sheet layer.
Further, in described composite, carbon coated ferriferrous oxide accounts for 30～70wt% of whole composite gross mass.If carbon coated ferriferrous oxide content is less than 30wt%, then owing to activity substance content is too low, gained composite entirety specific capacity declines, and when its content is more than 70wt%, the cushioning effect of Graphene weakens, material circulation poor performance.
Further, in described composite, the crystallite dimension of ferroso-ferric oxide is 8～100nm.
The preparation method that second technical problem that the invention solves the problems that is to provide above-mentioned composite, comprises the steps:
Step one, graphene oxide dispersion and bivalence source of iron stirring and evenly mixing form mixed liquor；Wherein, graphene oxide with the amount ratio of bivalence source of iron is: the bivalence source of iron that every 100mg graphene oxide uses iron content to be 1～10mmol；
Step 2, in step one gained mixed liquor, add tripolycyanamide and formalin, at least 3h is reacted under 160～200 DEG C of hydrothermal conditions, tripolycyanamide in-situ polymerization is made to obtain melamine resin, redox graphene simultaneously, it is thus achieved that redox graphene/ferrous ion/melamine resin composite；Wherein, the consumption of tripolycyanamide is with the Mass Calculation of graphene oxide in step one, and the quality of tripolycyanamide is 0.5～5 times of graphene oxide quality, and the consumption of formalin is 1g tripolycyanamide correspondence 1～5ml formalin；
Step 3, the redox graphene/ferrous ion/melamine resin composite of step 2 gained is transferred to pH > in the strong alkaline aqueous solution of 11, stand more than 0.5h, namely obtain the ferroso-ferric oxide/graphene composite material of melamine resin cladding, must do, then through washing, dried, ferroso-ferric oxide/graphene composite material that melamine resin is coated with；
Step 4, the ferroso-ferric oxide/graphene composite material being coated with by dry for gained in step 3 melamine resin are under inert gas shielding; high temperature sintering (purpose is carbonization melamine resin) at least 3h (being sintered in tube furnace) at 550～800 DEG C; obtain the ferroso-ferric oxide of carbon cladding and Graphene carried out N doping simultaneously, finally obtaining carbon coated ferriferrous oxide/nitrogen-doped graphene composite.
Further, in step one, described bivalence source of iron is ferrous chloride, ferrous nitrate, ferrous sulfate and one or more in other divalent iron salts.In the present invention, only with the ferrous iron source of iron as ferroso-ferric oxide, it is owing to ferrous iron can redox graphene under hydrothermal conditions.
In step, described graphene oxide dispersion is graphene oxide with distilled water by suspension that the concentration stirred and supersound process (mixing time is 15～25min about, it is preferred to 20min) obtains is 8～12mg/mL (preferably 10mg/mL).
Further, in step 3, adopt distilled water wash, the dry method adopting vacuum lyophilization；In the present invention, any drying means is all passable, and lyophilizing is more conducive to keep sample structure in aqueous.
Described vacuum freeze-drying method is: carry out vacuum lyophilization in-55～-45 DEG C (being preferably-50 DEG C) in freezer dryer.
The 3rd the invention solves the problems that technical problem is that and point out: gained carbon coated ferriferrous oxide of the present invention/nitrogen-doped graphene composite application in lithium ion battery anode active material.
The 4th technical problem that the invention solves the problems that is to provide a kind of lithium ion battery, and including positive electrode active materials and negative active core-shell material, described negative active core-shell material is carbon coated ferriferrous oxide of the present invention/nitrogen-doped graphene composite.
The invention have the advantages that
1, composite has higher circulation and high rate performance；It is applied to cathode material for high capacity lithium ion battery.
2, carbon coated ferriferrous oxide/nitrogen-doped graphene composite can not only effectively cushion ferroso-ferric oxide bulk effect in electrochemical reaction, also improve the electric conductivity of material simultaneously, it is substantially reduced the impedance of battery, thus being effectively improved the chemical property of material.
3, the preparation method of the present invention is simple, abundant raw material source, reaction condition gentle, easily operate.
The invention discloses a kind of carbon coated ferriferrous oxide/nitrogen-doped graphene composite and preparation method thereof and its application as high capacity lithium ion cells cathode active material.This negative material is made up of carbon coated ferriferrous oxide and nitrogen-doped graphene, gained melamine resin is carbon coated ferriferrous oxide after tripolycyanamide in-situ polymerization carbon source and the nitrogenous source of nitrogen-doped graphene；Carbon coated ferriferrous oxide is obtained, to improve the electric conductivity of ferriferrous oxide material through high temperature sintering in-situ carburization melamine resin；Meanwhile, Graphene is carried out N doping by high-temperature sintering process, introduce extra defect to provide site for the deintercalation of lithium ion more.When this composite is used as electrode material, battery table reveals the cycle performance of excellence, and experimental data proves, with 1000mAg-1Relatively high charge-discharge speed under, composite charge/discharge capacity can stably at 400mAhg-1.Additionally, the method that the present invention prepares lithium ion battery negative material, technique is simple, easily operates, and process safety, environmental protection, has industrialization potential.
Accompanying drawing explanation
Fig. 1 is the XRD (a) before and after embodiment 2 sintering and XPS (b) figure.
Fig. 2 is the N1s swarming spectrogram of sample XPS before and after embodiment 2 sintering.
Fig. 3 be embodiment 2 sintering before (a) and sintering after (b) SEM figure.
Fig. 4 is the cycle performance comparison diagram of embodiment and comparative example, and charging and discharging currents density is 1000mAhg-1。
Detailed description of the invention
The present invention is in aqueous, utilizes the home position polymerization reaction of tripolycyanamide, and melamine resin original position is formed graphene sheet layer surface, wraps up substantial amounts of iron ion simultaneously；By the pH value of regulation system, iron ion original position is made to form ferroso-ferric oxide, obtain melamine resin/ferroso-ferric oxide/graphene composite material, then by after composite lyophilizing, sinter melamine resin under inert gas atmosphere and namely obtain carbon coated ferriferrous oxide/nitrogen-doped graphene composite, the nitrogenous source of the melamine resin carbon source simultaneously as carbon coated ferriferrous oxide and nitrogen-doped graphene.
In the present invention, ferroso-ferric oxide introduces the Graphene class Carbon Materials with bigger serface, therefore the electrical conductivity of composite is not only increased, can highly desirable cushion ferroso-ferric oxide change in volume in the embedding de-process of lithium ion simultaneously, avoid caving in of electrode material, improve the cyclical stability of composite.In addition, ferroso-ferric oxide is carried out carbon and is coated with the interaction that can improve between itself and Graphene by the present invention, and carbon coated ferriferrous oxide can be prevented effectively from the reunion of ferroferric oxide nano granules itself, contribute to it and uniform and stable be dispersed in graphene sheet layer surface, the carbon-coating being simultaneously coated with can improve the electric charge transmission between ferroso-ferric oxide and Graphene, is conducive to the further raising of conductivity of composite material energy.
Embodiment 1
Tradition Hummers method is adopted to prepare graphene oxide.Ice-water bath assembles 250ml reaction bulb, add 23ml concentrated sulphuric acid, stirring is lower adds 2g natural flake graphite powder and 1g sodium nitrate, whole process temperature controls to react 2h below 4 DEG C, it is gradually added 6g potassium permanganate again, control reaction temperature less than 20 DEG C, stirring reaction 1h, then it is warmed up to about 35 DEG C and continues stirring 30min, it is slow added into 60ml deionized water, after stirring 20min, and add 25ml hydrogen peroxide (30Vol%) and react 15min and make solution become glassy yellow, and dissolve with 40mlHCl solution (10Vol%), centrifugation is also close neutral until pH value with deionized water wash, graphene oxide water solution lyophilizing (the vacuum that finally will obtain,-50 DEG C) obtain graphene oxide.
Step one, take graphene oxide 300mg and be dissolved in 30mL distilled water, stirring ultrasonic 20min, obtain unit for uniform suspension；
Step 2, addition Iron dichloride tetrahydrate 1g (5mmol) in the suspension of step one gained, stir 10min；
Step 3, in step 2 gained mixed liquor add 0.5g tripolycyanamide, stir 30min, add 1ml formalin, mixed solution transferred to 100ml polytetrafluoroethylene bushing, in water heating kettle 180 DEG C reaction 8h；
Step 4, step 3 gained product is filtered, solid product after filtration is transferred to 200mL concentration is in 30wt% ammonia (pH > 12), stand 1h, namely obtain ferroso-ferric oxide/melamine resin/graphene composite material, material is carried out frozen dried.
Step 5, by the ferroso-ferric oxide/melamine resin/graphene composite material after lyophilizing in tube furnace with 600 DEG C, under nitrogen protection sinter 5h, namely obtain carbon coated ferriferrous oxide/nitrogen and mix graphene composite material.
Embodiment 2
Step one, take graphene oxide 300mg and be dissolved in 30mL distilled water, stirring ultrasonic 20min, obtain unit for uniform suspension；
Step 2, addition Iron dichloride tetrahydrate 1g (5mmol) in the suspension of step one gained, stir 10min；
Step 3, in step 2 gained mixed liquor add 1.0g tripolycyanamide, stir 30min, add 2ml formalin, mixed solution transferred to 100ml polytetrafluoroethylene bushing, in water heating kettle 190 DEG C reaction 5h.
Step 4, step 3 gained product is filtered, the solid product after filtering is transferred in 200mL30wt% ammonia, stands 1h, namely obtain ferroso-ferric oxide/melamine resin/graphene composite material, material is carried out frozen dried.
Step 5, by the ferroso-ferric oxide/melamine resin/graphene composite material after lyophilizing in tube furnace with 700 DEG C, under nitrogen protection sinter 3h, namely obtain carbon coated ferriferrous oxide/nitrogen and mix graphene composite material.
Comparative example 1
Step one, take graphene oxide 300mg and be dissolved in 30mL distilled water, stirring ultrasonic 20min, obtain unit for uniform suspension；
Step 2, addition Iron dichloride tetrahydrate 1g (5mmol) in the suspension of step one gained, stir 10min；
Step 3, in step 2 gained mixed liquor add 2.0g tripolycyanamide, stir 30min, add 4ml formalin, mixed solution transferred to 100ml polytetrafluoroethylene bushing, in water heating kettle 200 DEG C reaction 3h.
Step 4, step 3 gained product is filtered, the solid product after filtering is transferred in 200mL30% ammonia, stands 1h, namely obtain ferroso-ferric oxide/melamine resin/graphene composite material, material is carried out frozen dried.
Step 5, by the ferroso-ferric oxide/melamine resin/graphene composite material after lyophilizing in tube furnace with 800 DEG C, under nitrogen protection sinter 3h, namely obtain carbon coated ferriferrous oxide/nitrogen and mix graphene composite material.
Comparative example 2
Step one, take graphene oxide dispersion 30mL, containing about 300mg graphene oxide, stirring ultrasonic 20min, obtain unit for uniform suspension；
Step 2, addition Iron dichloride tetrahydrate 1g (5mmol) in the suspension of step one gained, stir 10min；
Step 3, mixed solution is transferred to 100ml polytetrafluoroethylene bushing, 180 DEG C of reaction 10h in water heating kettle.
Step 4, step 3 gained product is filtered, the solid product after filtering is transferred in 200mL30wt% ammonia, stands 1h, namely obtain ferroso-ferric oxide/graphene composite material, material is carried out frozen dried.
Step 5, by the ferroso-ferric oxide/graphene composite material after lyophilizing in tube furnace with 700 DEG C, under nitrogen protection sinter 3h.
The composite that the present embodiment obtains is carbon coated ferriferrous oxide/nitrogen-doped graphene composite, in composite before and after sintering carbonization melamine resin, for embodiment 2, its XRD spectra (Fig. 1 (a)) all demonstrates the ferroso-ferric oxide crystal diffraction peak of standard, calculating according to XRD result and obtain ferroferric oxide nano granules size before high temperature sintering at 8～10nm, after sintering carbonization melamine resin, ferroferric oxide nano granules crystallite dimension is between 20～25nm.Mainly due to after high-temperature maturing processes, the crystallization further growth of ferroso-ferric oxide, crystallization is more sophisticated.Meanwhile, before and after sintering, XPS (Fig. 1 (the b)) data of sample are it can be seen that sample, equal essential element is C, O, Fe, N before and after sintering, and in the sample after burning, the relative amount of N element reduces, and at high temperature decomposes mainly due to melamine resin.The N1s of sample before and after sintering is carried out peak-fit processing to determine the different covalent bond combining forms of nitrogen element, from shown in Fig. 2, in sample before sintering, N1s spectrogram is mainly made up of the pyridine type nitrogen of the pyrroles's type nitrogen and 398.2eV place that are positioned at 400.0eV place, and the sample after sintering is except containing above two class nitrogen elements, there is also the graphitization nitrogen at 401.0eV place, after sintering is described, define nitrogen-doped graphene.
From scanning electron microscope (SEM) test result of embodiment 2 it can clearly be seen that, in sample before sintering, the melamine resin that in-situ polymerization obtains is uniformly coated on the surface (Fig. 3 (a)) of graphene sheet layer, after high temperature sintering carbonization melamine resin, the lamellar structure of Graphene can be observed directly, and it can be seen that the nano-particle of ferroso-ferric oxide is evenly distributed in the surface (Fig. 3 (b)) of whole graphene sheet layer.
Material embodiment and comparative example prepared is as lithium ion battery anode active material, and all the other steps of the preparation method of lithium ion battery are identical with common preparation method.The manufacture method of negative plate is as follows, is respectively adopted embodiment and material prepared by comparative example is active substance, and acetylene black is conductive agent, and PVDF is bonding agent.Active substance, conductive agent, bonding agent mass ratio be 80:10:10, they after mix homogeneously, are coated uniformly on Copper Foil in NMP (N-methyl ketopyrrolidine) solvent, and at 120 DEG C vacuum drying 24h, be cut into disk with microtome.With 1MLiPF6Being dissolved in as electrolyte in vinyl carbonate (EC) and dimethyl carbonate (DMC), lithium sheet is as positive pole, and Celgard2320 is barrier film, is assembled into CR2030 button cell and tests.
Table 1 embodiment compares (charging and discharging currents density=1C (1000mAg with comparative example cycle performance-1))
| 1st time | 20th time | 40th time | 60th time | 80th time | 100th time | |
| Embodiment 1 (mA h g-1) | 550 | 420 | 300 | 250 | 200 | 150 |
| Embodiment 2 (mA h g-1) | 420 | 420 | 400 | 400 | 380 | 350 |
| Comparative example 1 (mA h g-1) | 300 | 200 | 170 | 150 | 140 | 140 |
| Comparative example (mA h g-1) | 420 | 300 | 250 | 200 | 190 | 140 |
As shown in table 1, embodiment and comparative example are at 1C (1000mAg-1) carrying out the specific capacity of constant current charge-discharge test gained under electric current density, result shows, embodiment 2 has most stable of cycle performance, and in charge and discharge process, recycle ratio capacity maintains higher level all the time；Embodiment 1 gained sample shows higher first charge-discharge capacity, and however as the increase of cycle-index, its recycle ratio capacities chart reveals obvious decay, more mainly due to the content of ferroso-ferric oxide in system；Embodiment 3 shows relatively low first charge-discharge capacity, and along with cycle-index increase also shows the trend of capacity attenuation, it is the recycle ratio capacity first causing it relatively low owing to ferroso-ferric oxide content is relatively low on the one hand, it is owing to comparative example 1 sample introduces more melamine resin before sintering on the other hand, after melamine resin removes, connection between ferroso-ferric oxide and Graphene is destroyed, cause that the volume buffering effect of ferroso-ferric oxide is weakened by grapheme material, therefore cyclical stability declines, therefore the addition of tripolycyanamide is no more than 5 times of graphene oxide content.Comparative example 2 sample is the sample being not added with tripolycyanamide, but through the experimentation identical with embodiment sample, result shows, comparative example 2 sample shows the trend of obvious capacity attenuation, illustrates can be effectively improved after ferroso-ferric oxide/graphene composite material carries out carbon cladding and nitrogen cladding the cycle performance of material.
Claims (10)
1. composite, it is characterised in that described composite is made up of carbon coated ferriferrous oxide and nitrogen-doped graphene, in described composite, ferroso-ferric oxide is evenly distributed in the surface of graphene sheet layer.
2. composite according to claim 1, it is characterised in that in described composite, carbon coated ferriferrous oxide accounts for 30～70wt% of composite gross mass.
3. composite according to claim 1 and 2, it is characterised in that in described composite, ferroso-ferric oxide crystallite dimension is 8～100nm.
4. the preparation method of composite described in any one of claims 1 to 3, it is characterised in that comprise the steps:
Step one, graphene oxide dispersion and bivalence source of iron stirring and evenly mixing form mixed liquor；Wherein, graphene oxide with the amount ratio of bivalence source of iron is: the bivalence source of iron that every 100mg graphene oxide uses iron content to be 1～10mmol；
Step 2, in step one gained mixed liquor, add tripolycyanamide and formalin, at least 3h is reacted under 160～200 DEG C of hydrothermal conditions, tripolycyanamide in-situ polymerization is made to obtain melamine resin, redox graphene simultaneously, it is thus achieved that redox graphene/ferrous ion/melamine resin composite；Wherein, the consumption of tripolycyanamide is with the Mass Calculation of graphene oxide in step one, and the quality of tripolycyanamide is 0.5～5 times of graphene oxide quality, and the consumption of formalin is 1g tripolycyanamide correspondence 1～5ml formalin；
Step 3, the redox graphene/ferrous ion/melamine resin composite of step 2 gained is transferred to pH > in the strong alkaline aqueous solution of 11, stand more than 0.5h, namely obtain the ferroso-ferric oxide/graphene composite material of melamine resin cladding, must do, then through washing, dried, ferroso-ferric oxide/graphene composite material that melamine resin is coated with；
Step 4, the ferroso-ferric oxide/graphene composite material being coated with by dry for gained in step 3 melamine resin are under inert gas shielding; high temperature sintering at least 3h at 550～800 DEG C; obtain the ferroso-ferric oxide of carbon cladding and Graphene carried out N doping simultaneously, finally obtaining carbon coated ferriferrous oxide/nitrogen-doped graphene composite.
5. the preparation method of composite according to claim 4, it is characterised in that in step one, described bivalence source of iron is ferrous chloride, ferrous nitrate, ferrous sulfate and one or more in other divalent iron salts.
6. the preparation method of composite according to claim 4 or 5, it is characterised in that in step one, described graphene oxide dispersion is the suspension that graphene oxide is obtained by stirring supersound process with distilled water.
7. the preparation method of composite according to claim 6, it is characterised in that stirring sonication treatment time is 15～25min, and the concentration of gained suspension is 8～12mg/mL.
8. the preparation method of composite according to any one of claim 4～7, it is characterised in that in step 3, adopts distilled water wash, the dry method adopting vacuum lyophilization；Further, described vacuum freeze-drying method is: carry out vacuum lyophilization in-55～-45 DEG C in freezer dryer.
9. composite application in lithium ion battery anode active material, described composite is the composite described in any one of claims 1 to 3；Or described composite adopts the method described in any one of claim 4～8 to prepare.
10. lithium ion battery, including positive electrode active materials and negative active core-shell material, it is characterised in that described negative active core-shell material is the composite described in any one of claims 1 to 3；Or described negative electrode active material adopts the method described in any one of claim 4～8 to prepare.
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| CN106207126A (en) * | 2016-08-25 | 2016-12-07 | 陕西科技大学 | A kind of Fe3o4the preparation method of the lithium ion battery negative material of/rGO sandwich structure |
| CN106532001A (en) * | 2016-12-01 | 2017-03-22 | 陕西科技大学 | Preparation method of nitrogen-doping carbon substrate-supported Fe3O4 composite material sodium-ion battery negative electrode material |
| CN106848303A (en) * | 2017-01-17 | 2017-06-13 | 陕西科技大学 | A kind of preparation method of graphene-supported graphite carbon coated ferriferrous oxide lithium ion battery negative material |
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| CN109755570A (en) * | 2017-11-06 | 2019-05-14 | 北京碳阳科技有限公司 | Three-dimensional combination electrode material and preparation method thereof, electrode and energy storage device |
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| CN113871209B (en) * | 2021-08-30 | 2023-05-26 | 兰州大学 | Carbon-coated graphene-ferric oxide composite electrode material and preparation method and application thereof |
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