CN103854881B - A kind of preparation method of graphene/carbon nano-tube combination electrode - Google Patents
A kind of preparation method of graphene/carbon nano-tube combination electrode Download PDFInfo
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Abstract
The invention belongs to electrode preparation field, it discloses the preparation method of a kind of graphene/carbon nano-tube combination electrode, including step: soaked in strong acid by CNT, reflow treatment, obtain chloride CNT；Then by chloride CNT reflow treatment in ethylenediamine and toluene mixed solution, amidatioon CNT is obtained；Amidatioon CNT and graphene oxide are each configured to dispersion liquid, finally by collector alternate immersion in amidatioon CNT and graphene oxide dispersion, obtain combination electrode after drying.The present invention provides the preparation method of graphene/carbon nano-tube combination electrode, use the mode of LBL self-assembly, manufacturing process avoids the agglomeration traits between graphene sheet layer, improve the electric double layer capacity of material, CNT can carry out electronics conduction between layers at Graphene simultaneously, it is ensured that electrode material has height power density.
Description
Technical field
The present invention relates to the preparation of electrode, particularly relate to the preparation method of a kind of graphene/carbon nano-tube combination electrode.
Background technology
Grapheme material was prepared in 2004, owing to structure and the photoelectric property of its uniqueness receive people and pay attention to widely in peace moral strong K sea nurse (Andre K.Geim) etc. of Univ Manchester UK.Mono-layer graphite due to its big specific surface area, excellent conduction, heat conductivility and low thermal coefficient of expansion and be considered as preferable material.As: 1, high intensity, Young mole, (1,100GPa), fracture strength: (125GPa)；2, high heat conductance, (5,000W/mK)；3, high conductivity, carrier transport rate, (200,000cm2/V*s)；4, high specific surface area, (calculated value: 2,630m2/g).Especially its high connductivity character, the structural property of the nanoscale of big specific surface character and its monolayer two dimension, electrode material can be used as in ultracapacitor and lithium ion battery.Up to the present, the known method preparing Graphene has multiple, such as: (1) micromechanics stripping method.This method can only produce quantity and be extremely limited graphene film, can based on study；(2) ultrahigh vacuum Graphene epitaxial growth method.The high cost of this method and the structure of sequin limit its application；(3) chemical vapour deposition technique (CVD).The method can meet scale and prepare the requirement of high-quality graphene, but relatively costly, complex process.(4) solvent stripping method.The method shortcoming is that productivity is the lowest, limits its business application；(5) oxidation-reduction method.
Ruoff group utilizes the Graphene of chemical modification as electrode material, tests the performance of ultracapacitor based on Graphene.The capacitive property of this grapheme material capacity in water system and organic electrolyte can reach 135F/g and 99F/g respectively.Rao et al. compares the capacitive property of the Graphene prepared by two kinds of methods.In sulfuric acid electrolyte, the Graphene obtained by graphite oxide dilatometry and Nano diamond conversion method has higher capacity, can reach 117F/g;In organic electrolyte, the when that voltage being 3.5V, its capacity and energy density can reach 71F/g and 31.9Wh/kg.
Above method is all that the graphene powder using preparation makes electrode slice through techniques such as batch mixing, coating, roll-in, sections, in the preparation of Graphene and the problem of the reunion being constantly present grapheme material during making pole piece, and then after making battery, affecting the energy density of battery, the actual energy density of grapheme material is far smaller than its theoretical value.
Summary of the invention
Based on the problems referred to above, to be solved by this invention it has a problem in that the preparation method that a kind of graphene/carbon nano-tube combination electrode is provided.
Technical scheme is as follows:
The preparation method of a kind of graphene/carbon nano-tube combination electrode, comprises the steps:
Reflux in strong acid at 50-80 DEG C 0.5-2h by CNT, then filters, and by the screening obtained through wash, filtering, dry, obtain carboxylic carbon nano-tube；Wherein, CNT is 0.1-2g:100ml with the solid-to-liquid ratio of strong acid；
Described carboxylic carbon nano-tube is being added chloride reagent, and reflux at 50-80 DEG C 5-15h, obtains chloride CNT；Wherein, carboxylic carbon nano-tube is 0.1-2g:100ml with the solid-to-liquid ratio of chloride reagent；
Described chloride CNT and amidation reagent are added in organic solvent, and at 50-80 DEG C, reacts 24-48h, filter subsequently, and by the screening that obtains through ethanol and washing, dried, obtain amidatioon CNT；Wherein, chloride CNT: amidation reagent: the solid-to-liquid ratio of organic solvent is 0.1-1g:100:200ml；
Described chloride CNT is added to the water ultrasonic disperse, forms the amidatioon carbon nano tube dispersion liquid of 0.2-0.8mg/ml；Meanwhile, graphite oxide is added to the water ultrasonic disperse, forms the graphene oxide dispersion of 0.2-0.8mg/ml；
Collector is soaked 30 ~ 60min at amidatioon carbon nano tube dispersion liquid, in described graphene oxide dispersion, soaks 1 ~ 5min the most again；Alternate immersion 30 ~ 500 times in amidatioon carbon nano tube dispersion liquid and dispersion liquid the most again, and in every kind of dispersion liquid, soak time is 1 ~ 5min, obtains graphene oxide/carbon nano-tube combination electrode after drying；
By described graphene oxide/carbon nano-tube combination electrode under inert gas shielding, in 500 ~ 1000 DEG C of pyroreaction 1 ~ 5h, after cooling, obtain described graphene/carbon nano-tube electrode slice.
The preparation method of described graphene/carbon nano-tube combination electrode, wherein, the mixed acid that described strong acid is 68% concentrated nitric acid and 98% concentrated sulphuric acid is mixed to get according to the volume ratio of 3:1.
The preparation method of described graphene/carbon nano-tube combination electrode, wherein, described chloride reagent is dichloro Asia phenol, phosphorus oxychloride or thionyl chloride.
The preparation method of described graphene/carbon nano-tube combination electrode, wherein, described amidation reagent is ethylenediamine, triethylamine or carbamide.
The preparation method of described graphene/carbon nano-tube combination electrode, wherein, described organic solvent is dry toluene, oxolane or dichloromethane.
The preparation method of described graphene/carbon nano-tube combination electrode, wherein, described collector is aluminium foil, nickel screen, titanium foil or steel foil.
The preparation method of described graphene/carbon nano-tube combination electrode, wherein, dry in described chloride CNT preparation process is 50 DEG C of dry 24h in vacuum drying oven.
The preparation method of described graphene/carbon nano-tube combination electrode, wherein, described noble gas is one or more in nitrogen, argon, helium and neon.
The present invention provides the preparation method of graphene/carbon nano-tube combination electrode, use the mode of LBL self-assembly, grapheme material is prepared as electrode slice, the electrode slice of preparation can be used as the positive plate of lithium ion battery or battery capacitor, the agglomeration traits between graphene sheet layer is avoided during making electrode slice, improving the electric double layer capacity of material, CNT can carry out electronics conduction between layers at Graphene simultaneously, it is ensured that electrode material has height power density；Binding agent needed for also the method does not the most add the preparation of usual electrode simultaneously and conductive agent.
Accompanying drawing explanation
Fig. 1 is the preparation technology flow chart of graphene/carbon nano-tube combination electrode of the present invention.
Detailed description of the invention
The present invention provides the preparation method of a kind of graphene/carbon nano-tube combination electrode, as it is shown in figure 1, its technological process is as follows:
(1), by CNT 50-80 DEG C of backflow 0.5-2h in strong acid (68% concentrated nitric acid: the mixed acid that 98% concentrated sulphuric acid=3:1 obtains), then the product obtained is washed, filters, is dried to obtain carboxylic carbon nano-tube；Wherein, CNT is 0.1-2g:100ml with the solid-to-liquid ratio of mixed acid；
(2), by the carboxylic carbon nano-tube that obtains in chloride reagent, 50-80 DEG C of backflow 5-15h, obtain chloride CNT；Wherein, carboxylic carbon nano-tube is 0.1-2g:100ml with the solid-to-liquid ratio of chloride reagent；
Preferably, chloride reagent is dichloro Asia phenol, phosphorus oxychloride or thionyl chloride；
(3) above-mentioned chloride CNT and amidation reagent are added in organic solvent, 50-80 DEG C of reaction 24-48h, filters subsequently, and by the screening that obtains after ethanol and washing, 50 DEG C of vacuum drying 24h, obtains amidatioon CNT；Wherein, chloride CNT: amidation reagent: the solid-to-liquid ratio of organic solvent is 0.1-1g:100:200ml；
Preferably, amidation reagent is ethylenediamine, triethylamine or carbamide；
Preferably, organic solvent is dry toluene, oxolane or dichloromethane；
(4), by described amidatioon CNT it is added to the water ultrasonic disperse, forms the amidatioon carbon nano tube dispersion liquid of 0.2-0.8mg/ml；Meanwhile, graphite oxide is added to the water ultrasonic disperse, forms the graphene oxide dispersion of 0.2-0.8mg/ml；
(5) in amidatioon carbon nano tube dispersion liquid, by collector first soak 30 ~ 60min, in described graphene oxide dispersion, soak 1 ~ 5min the most again；Alternate immersion 30 ~ 500 times in amidatioon carbon nano tube dispersion liquid and graphene oxide dispersion the most successively, and in every kind of dispersion liquid, soak time is 1 ~ 5min, obtains graphene oxide/carbon nano-tube combination electrode after drying；
(6), by described graphene oxide/carbon nano-tube combination electrode under inert gas shielding, in 500 ~ 1000 DEG C of pyroreaction 1 ~ 5h, after cooling, carry out roll-in, obtain described graphene/carbon nano-tube electrode slice.
In above-mentioned steps (5), collector can be selected for aluminium foil, nickel screen, titanium foil, steel foil etc..
In above-mentioned steps (6), noble gas can be one or more mixing in nitrogen, argon, helium and neon.
The present invention provides the preparation method of graphene/carbon nano-tube combination electrode, use the mode of LBL self-assembly, grapheme material is prepared as electrode slice, the electrode slice of preparation can be used as the positive plate of lithium ion battery or battery capacitor, the agglomeration traits between graphene sheet layer is avoided during making electrode slice, improving the electric double layer capacity of material, CNT can carry out electronics conduction between layers at Graphene simultaneously, it is ensured that electrode material has height power density；Binding agent needed for also the method does not the most add the preparation of usual electrode simultaneously and conductive agent.
Below in conjunction with the accompanying drawings, presently preferred embodiments of the present invention is described in further detail.
Embodiment 1
(1) by CNT 50 DEG C of backflow 2h in mixed acid (68% concentrated nitric acid: 98% concentrated sulphuric acid=3:1), then the product obtained is washed, filters, is dried to obtain carboxylic carbon nano-tube；CNT is 0.1g:100ml with the solid-to-liquid ratio of mixed acid；
(2) by the carboxylic carbon nano-tube that obtains at dichloro Asia phenol (SOCl2In), 50 DEG C of backflow 15h, obtain chloride CNT；Carboxylic carbon nano-tube is 0.1g:100ml with the solid-to-liquid ratio of SOCl2；
(3) by above-mentioned chloride CNT and ethylenediamine 50 DEG C of reaction 24h in dry toluene, ethanol and washing, after 50 DEG C of vacuum drying 24h, amidatioon CNT is obtained；Chloride CNT: ethylenediamine: the addition of dry toluene is 0.1g:100ml:200ml；
(4) chloride CNT ultrasonic disperse is formed in water the amidatioon carbon nano tube dispersion liquid of 0.2mg/ml；
(5) graphite oxide ultrasonic disperse is formed in water the graphene oxide dispersion of 0.2mg/ml；
(6) first aluminium foil is soaked in chloride carbon nano tube dispersion liquid 30min, then disperse 1min in graphene oxide dispersion；Alternate immersion in chloride carbon nano tube dispersion liquid disperses with graphene oxide dispersion the most successively, in every kind of dispersion liquid, soak time is 1min, obtains electrode after drying；
(7) electrode slice obtained is placed with in the Muffle furnace of nitrogen gas protection, 500 DEG C of pyroreactions 5h, carries out roll-in after cooling, obtain graphene/carbon nano-tube electrode slice.
Embodiment 2
(1) by CNT 80 DEG C of backflow 0.5h in mixed acid (68% concentrated nitric acid: 98% concentrated sulphuric acid=3:1), then the product obtained is washed, filters, is dried to obtain carboxylic carbon nano-tube；CNT is 2g:100ml with the addition of mixed acid；
(2) the carboxylic carbon nano-tube 80 DEG C of backflow 5h in phosphorus oxychloride that will obtain, obtain chloride CNT；Carboxylic carbon nano-tube is 2g:100ml with the solid-to-liquid ratio of phosphorus oxychloride；
(3) by above-mentioned chloride CNT and triethylamine 80 DEG C of reaction 48h in oxolane, ethanol and washing, after 50 DEG C of vacuum drying 24h, amidatioon CNT is obtained；Chloride CNT: triethylamine: the solid-to-liquid ratio of oxolane is 1g:100ml:200ml；
(4) chloride CNT ultrasonic disperse is formed in water the amidatioon carbon nano tube dispersion liquid of 0.8mg/ml；
(5) graphite oxide ultrasonic disperse is formed in water the graphene oxide dispersion of 0.8mg/ml；
(6) first nickel screen is soaked in chloride carbon nano tube dispersion liquid 60min, then soak 5min in graphene oxide dispersion；Alternate immersion 50 times in amidatioon carbon nano tube dispersion liquid and graphene oxide dispersion the most successively, in every kind of dispersion liquid, soak time is 5min, obtains electrode after drying；
(7) electrode slice obtained is placed with in the Muffle furnace of argon gas protection, 1000 DEG C of pyroreactions 1h, carries out roll-in after cooling, obtain graphene/carbon nano-tube electrode slice.
Embodiment 3
(1) by CNT 60 DEG C of backflow 1h in mixed acid (68% concentrated nitric acid: 98% concentrated sulphuric acid=3:1), then the product obtained is washed, filters, is dried to obtain carboxylic carbon nano-tube；CNT is 0.8g:100ml with the solid-to-liquid ratio of mixed acid；
(2) the carboxylic carbon nano-tube 60 DEG C of backflow 8h in thionyl chloride that will obtain, obtain chloride CNT；Carboxylic carbon nano-tube is 0.8g:100ml with the solid-to-liquid ratio of thionyl chloride；
(3) by above-mentioned chloride CNT and carbamide 60 DEG C of reaction 30h in dichloromethane, ethanol and washing, after 50 DEG C of vacuum drying 24h, amidatioon CNT is obtained；Chloride CNT: carbamide: the solid-to-liquid ratio of dichloromethane is 0.4g:100ml:200ml；
(4) amidatioon CNT ultrasonic disperse is formed in water the amidatioon carbon nano tube dispersion liquid of 0.4mg/ml；
(5) graphite oxide ultrasonic disperse is formed in water the graphene oxide dispersion of 0.4mg/ml；
(6) first titanium foil is soaked in amidatioon carbon nano tube dispersion liquid 40min, then soak 2min in graphene oxide dispersion；Alternate immersion 500 times in amidatioon carbon nano tube dispersion liquid and graphene oxide dispersion the most successively, in every kind of dispersion liquid, soak time is 2min, obtains electrode after drying；
(7) electrode slice obtained is placed with in the Muffle furnace of helium atmosphere protection, 800 DEG C of pyroreactions 2h, carries out roll-in after cooling, obtain graphene/carbon nano-tube electrode slice.
Embodiment 4
(1) by CNT 70 DEG C of backflow 1.5h in mixed acid (68% concentrated nitric acid: 98% concentrated sulphuric acid=3:1), then the product obtained is washed, filters, is dried to obtain carboxylic carbon nano-tube；CNT is 1.5g:100ml with the solid-to-liquid ratio of mixed acid；
(2) by the carboxylic carbon nano-tube that obtains at SOCl2In (dichloro Asia phenol), 70 DEG C of backflow 12h, obtain chloride CNT；Carboxylic carbon nano-tube and SOCl2Solid-to-liquid ratio be 1.5g:100ml；
(3) by above-mentioned chloride CNT and ethylenediamine 70 DEG C of reaction 36h in dry toluene, ethanol and washing, after 50 DEG C of vacuum drying 24h, amidatioon CNT is obtained；Chloride CNT is 0.7g:100ml:200ml with ethylenediamine, the solid-to-liquid ratio of dry toluene；
(4) amidatioon CNT ultrasonic disperse respectively is formed in water the amidatioon carbon nano tube dispersion liquid of 0.6mg/ml；
(5) graphite oxide ultrasonic disperse is formed in water the graphene oxide dispersion of 0.6mg/ml；
(6) first steel foil is soaked in amidatioon carbon nano tube dispersion liquid 50min, then soak 3min in graphene oxide dispersion；Alternate immersion 200 times in amidatioon carbon nano tube dispersion liquid and graphene oxide dispersion the most successively, in every kind of dispersion liquid, soak time is 3min, obtains electrode after drying；
(7) electrode slice obtained is placed with in the Muffle furnace of neon gas shield, 700 DEG C of pyroreactions 3h, carries out roll-in after cooling, obtain graphene/carbon nano-tube electrode slice.
Embodiment 5
(1) by CNT 70 DEG C of backflow 1.5h in mixed acid (68% concentrated nitric acid: 98% concentrated sulphuric acid=3:1), then the product obtained is washed, filters, is dried to obtain carboxylic carbon nano-tube；CNT is 1.5g:100ml with the solid-to-liquid ratio of mixed acid；
(2) by the carboxylic carbon nano-tube that obtains at SOCl2In (dichloro Asia phenol), 70 DEG C of backflow 12h, obtain chloride CNT；Carboxylic carbon nano-tube and SOCl2Solid-to-liquid ratio be 1.5g:100ml；
(3) by above-mentioned chloride CNT and ethylenediamine 70 DEG C of reaction 36h in dry toluene, ethanol and washing, after 50 DEG C of vacuum drying 24h, amidatioon CNT is obtained；Chloride CNT is 0.7g:100ml:200ml with ethylenediamine, the solid-to-liquid ratio of dry toluene；
(4) amidatioon CNT ultrasonic disperse is formed in water the amidatioon carbon nano tube dispersion liquid of 0.6mg/ml；
(5) graphite oxide ultrasonic disperse is formed in water the graphene oxide dispersion of 0.6mg/ml；
(6) first aluminium foil is soaked in amidatioon carbon nano tube dispersion liquid 45min, then soak 4min in graphene oxide dispersion；Alternate immersion 400 times in amidatioon carbon nano tube dispersion liquid and graphene oxide dispersion the most successively, in every kind of dispersion liquid, soak time is 4min, obtains electrode after drying；
(7) electrode slice obtained is placed with in the Muffle furnace of argon gas protection, 600 DEG C of pyroreactions 4h, carries out roll-in after cooling, obtain graphene/carbon nano-tube electrode slice.
Comparative example 1
The preparation method of conventional electrodes sheet: be 1000m by specific surface area2/ g Graphene mixes with the ratio of mass ratio 90:5:5 with conductive agent acetylene black, binding agent PVDF, obtains active slurry, is coated on aluminium foil by active slurry, and after being dried 24h, tabletting obtains electrode slice.
The button cell that electrode slice prepared by above example and comparative example and lithium sheet and barrier film are assembled into carries out constant current charge-discharge test, and electrolyte uses ionic liquid BMIMBF4.The capacity obtaining embodiment is as follows:
Table 1 obtains battery energy density test result for each embodiment and comparative example.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | |
| Energy density wh/kg | 112 | 99 | 103 | 107 | 110 | 60 |
As shown in Table 1, the electrode material energy density using the present invention to prepare can reach about 110wh/kg, the electrode slice prepared higher than conventional method in comparative example 1, highest energy density 85.6wh/kg reported also above current document.
It should be appreciated that the above-mentioned statement for present pre-ferred embodiments is more detailed, therefore can not be considered the restriction to scope of patent protection of the present invention, the scope of patent protection of the present invention should be as the criterion with claims.
Claims (8)
1. the preparation method of a graphene/carbon nano-tube combination electrode, it is characterised in that include as
Lower step:
Reflux at 50-80 DEG C in strong acid 0.5-2h by CNT, then filters, and will obtain
Screening through washing, filtering, be dried, obtain carboxylic carbon nano-tube；Wherein, CNT and strong acid
Solid-to-liquid ratio be 0.1-2g:100ml；
Described carboxylic carbon nano-tube is being added chloride reagent, and reflux at 50-80 DEG C 5-15h,
Obtain chloride CNT；Wherein, carboxylic carbon nano-tube with chloride reagent solid-to-liquid ratio is
0.1-2g:100ml；
Described chloride CNT is added in organic solvent with amidation reagent, and at 50-80 DEG C
Reaction 24-48h, filters subsequently, and by the screening that obtains through ethanol and washing, dried, obtains acyl
Amination CNT；Wherein, chloride CNT: amidation reagent: the solid-to-liquid ratio of organic solvent
For 0.1-1g:100ml:200ml；
Described amidatioon CNT is added to the water ultrasonic disperse, forms the amide of 0.2-0.8mg/ml
Carbon nano tube dispersion liquid；Meanwhile, graphite oxide is added to the water ultrasonic disperse, forms 0.2-0.8mg/ml
Graphene oxide dispersion；
Collector is soaked 30～60min at amidatioon carbon nano tube dispersion liquid, the most again in described oxidation
Graphene dispersing solution soaks 1～5min；The most successively at amidatioon carbon nano tube dispersion liquid and
Alternate immersion 30～500 times in graphene oxide dispersion, and soak time is in every kind of dispersion liquid
1～5min, obtain graphene oxide/carbon nano-tube combination electrode after drying；
By described graphene oxide/carbon nano-tube combination electrode under inert gas shielding, in
500～1000 DEG C of pyroreactions 1～5h, after cooling, obtain described graphene/carbon nano-tube electrode slice.
The preparation method of graphene/carbon nano-tube combination electrode the most according to claim 1, its
Being characterised by, described strong acid is 68% concentrated nitric acid and 98% concentrated sulphuric acid mixes according to the volume ratio of 3:1
The mixed acid arrived.
The preparation method of graphene/carbon nano-tube combination electrode the most according to claim 1, its
Being characterised by, described chloride reagent is dichloro Asia phenol, phosphorus oxychloride or thionyl chloride.
The preparation method of graphene/carbon nano-tube combination electrode the most according to claim 1, its
Being characterised by, described amidation reagent is ethylenediamine, triethylamine or carbamide.
The preparation method of graphene/carbon nano-tube combination electrode the most according to claim 1, its
Being characterised by, described organic solvent is dry toluene, oxolane or dichloromethane.
The preparation method of graphene/carbon nano-tube combination electrode the most according to claim 1, its
Being characterised by, described collector is aluminium foil, nickel screen, titanium foil or steel foil.
The preparation method of graphene/carbon nano-tube combination electrode the most according to claim 1, its
Being characterised by, dry in described amidatioon CNT preparation process is in vacuum drying oven 50 DEG C
It is dried 24h.
The preparation method of graphene/carbon nano-tube combination electrode the most according to claim 1, its
Being characterised by, described noble gas is one or more in nitrogen, argon, helium and neon.
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| CN105244190A (en) * | 2015-10-21 | 2016-01-13 | 山东科技大学 | Preparation method of graphene/carbon nano tube co-reinforced conducting polymer hydrogel |
| CN106129374B (en) * | 2016-08-26 | 2019-08-27 | 深圳博磊达新能源科技有限公司 | A kind of transition metal oxide/binary carbon net anode composite material and aluminium ion battery |
| CN106442668B (en) * | 2016-09-28 | 2019-06-14 | 北京农学院 | A kind of preparation method of carbon nano tube modified electrode |
| CN106784700B (en) * | 2016-12-27 | 2020-02-18 | 电子科技大学 | Multilayer silicon/graphene composite lithium battery cathode material and preparation method thereof |
| CN106848313A (en) * | 2017-01-19 | 2017-06-13 | 深圳市金百纳纳米科技有限公司 | A kind of composite of one-dimensional graphene material |
| CN106935312B (en) * | 2017-03-29 | 2018-09-28 | 浙江师范大学 | A kind of aqueous mixed type electrocondution slurry and preparation method thereof |
| CN107146889B (en) * | 2017-04-24 | 2019-06-28 | 西北工业大学 | A kind of graphene/CNTs hybrid does lithium metal battery collector and preparation method thereof |
| CN108152353B (en) * | 2017-12-31 | 2020-05-12 | 西北师范大学 | Preparation of graphene-based carboxymethyl cellulose nanocrystalline composite material and application of graphene-based carboxymethyl cellulose nanocrystalline composite material as chiral recognition material |
| CN113174117B (en) * | 2021-04-26 | 2022-04-12 | 广东粤港澳大湾区黄埔材料研究院 | Dual-functional-layer polymer composite material and preparation method thereof |
| CN113488654B (en) * | 2021-07-27 | 2022-04-19 | 深圳齐锂纳米科技有限公司 | Graphene composite layered conductive agent supported by carbon nano tube |
| CN114156445B (en) * | 2021-10-28 | 2023-12-19 | 西安交通大学 | Electrode material with bionic shell lamellar structure and preparation method and application thereof |
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