CN105217617A - A kind of preparation method of three-D nano-porous Graphene - Google Patents
A kind of preparation method of three-D nano-porous Graphene Download PDFInfo
- Publication number
- CN105217617A CN105217617A CN201510688992.6A CN201510688992A CN105217617A CN 105217617 A CN105217617 A CN 105217617A CN 201510688992 A CN201510688992 A CN 201510688992A CN 105217617 A CN105217617 A CN 105217617A
- Authority
- CN
- China
- Prior art keywords
- nano
- preparation
- temperature
- hydrogen
- argon gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention provides a kind of preparation method of three-D nano-porous Graphene, comprise the following steps: preparation Cu-Mn alloy foil sheet; Carry out removal alloying process, obtain nanoporous copper foil; Preparing three-D nano-porous Graphene method is: under the atmosphere of argon gas, hydrogen, be warming up to 200-400 DEG C; Pass into acetylene and carry out growth hydrogenation graphite; Under the atmosphere of hydrogen, furnace temperature is risen to 500-1100 DEG C, rise to until furnace temperature and quartz boat is quickly moved to flat-temperature zone in the middle part of reaction tubes after assigned temperature and calcines; Under the atmosphere of hydrogen, sample is down to room temperature after calcining; Immerse in corrosive fluid and nano porous copper is removed, after cleaning, obtain the three-D nano-porous graphene film of self-supporting.This preparation method's technological process is simple, with low cost, the three-D nano-porous Graphene even aperture distribution of gained and all at nano-grade size, applicable suitability for industrialized production.
Description
Technical field
The invention belongs to the preparing technical field of nano material, be specifically related to a kind of preparation method of three-D nano-porous Graphene.
Background technology
Graphene is that its theoretical specific surface area reaches 2620m by the tightly packed individual layer Two-dimensional Carbon material of carbon atom
2/ g, and there is the performance such as electricity, optics, machinery admirably, therefore there is application prospect widely.At present, mechanically peel method, epitaxial growth method, chemical Vapor deposition process and chemical reduction method etc. all can prepare the derivative after Graphene and functionalization thereof.Integrate two-dimensional graphene and build the Graphene with specific three dimensional structure, and then the functional device of processability excellence is significant for the macroscopic view application of expanding Graphene.Three-dimensional structure can give the character of Graphene uniqueness, such as snappiness, porousness, high reactivity specific surface area etc.Therefore, the preparations and applicatio research of recent domestic to three-dimensional grapheme material is very active.
Up to now, investigators have established the multiple method preparing three-dimensional grapheme, such as, and the hot method of directed flow construction from part, solvent/water, substrate interface construction from part etc.But all there is a lot of problem in above several method:
(1) above several method all relies on the graphene oxide (rGO) of reduction to be raw material, and between the electroconductibility of rGO and desirable two-dimensional graphene, there is a big difference, and therefore, the three-dimensional grapheme performance obtained in order to upper method will be had a greatly reduced quality.
(2) rGO nanometer sheet is very easy to again pile up reunion in formation three-dimensional grapheme configuration process, and how intact the lamella character of maintenance rGO remain difficult point;
(3) microporous structure of the three-dimensional grapheme material assembled by rGO nanometer sheet mostly by occurring at random in 2D Graphene integration process, pore structure controllability and poor repeatability;
(4) the three-dimensional grapheme aperture size that above several method obtains exceedes Nano grade all, is not three-D nano-porous Graphene truly.
Chemical Vapor deposition process (CVD) is the most effectual way preparing high-quality graphene at present, therefore be also the most effective means of the three-D nano-porous Graphene of preparation, but, the aperture of three-dimensional grapheme material prepared by current utilization CVD is normally between hundreds of nanometer is to tens microns, but the still rare achievement in research with nanoscale pore structure three-dimensional Graphene.Therefore, find a kind of suitable matrix to obtain three-D nano-porous Graphene is the direction that scientist makes great efforts always.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of take nano porous metal as the method that matrix prepares three-D nano-porous Graphene, this preparation method's technological process is simple, with low cost, the three-D nano-porous Graphene even aperture distribution of gained and all at nano-grade size, be applicable to suitability for industrialized production.Technical scheme of the present invention is as follows:
Nano porous metal prepares a method for three-D nano-porous Graphene, and this preparation method adopts following technique:
1) nano porous metal paillon foil is prepared
Thickness is selected to be the Cu of 10-200um
30mn
70, Ni
30mn
70or Ni
xcu
30-xmn
70the alloy foil sheet of (x=5,10,15,20,25), carries out removal alloying process, obtains the nano porous metal paillon foil with the nano-porous structure of level with removal alloying time and removal alloying corrosive fluid change in concentration;
2) the many Graphenes of three-dimensional manometer are prepared
Quartz boat put into by the nano porous metal paillon foil that step 2 is obtained, quartz boat is placed in reaction tubes burner hearth external region, pass into carbon-source gas, argon gas and hydrogen, the ratio of carbon source, argon gas and hydrogen presses the flow configuration of 1-50:200-500:50-200, now furnace temperature is risen to 500-1100 DEG C, rise to after assigned temperature until furnace temperature and quartz boat is quickly moved to flat-temperature zone in the middle part of reaction tubes, calcine 0.5-30 minute at this temperature;
After calcining, quartz boat is moved to burner hearth outside from flat-temperature zone in the middle part of reaction tubes fast, and bell is opened, under the atmosphere of argon gas, sample is down to room temperature; Then sample is taken out from tube furnace, immerse in corrosive fluid and nano porous metal is removed, clean up afterwards and can obtain the three-D nano-porous graphene film of self-supporting.
Carbon-source gas is wherein acetylene, methane or ethene.
Compared with prior art, the present invention is matrix with nano porous metal, utilizes CVD, under the katalysis of nano porous metal, carbon source is catalyzed into Graphene, and namely nano porous metal removing obtains the three-D nano-porous Graphene of self-supporting the most at last.The inventive method has following advantage: (1) technique is simple, with low cost.One step can synthesize three-D nano-porous Graphene, simplifies technical process, has greatly saved cost; (2) pollution-free, environmental friendliness.The method of current assembling three-dimensional manometer Graphene utilizes the graphene oxide of reduction for raw material usually, and will use strong acid or other noxious chemicals in redox graphene preparation process, easily causes environmental pollution.The present invention is without any need for chemistry or physical treatment, and whole process is carried out under the environment of stable close friend, is a kind of green technology; (3) CVD of the present invention prepares three-D nano-porous Graphene technical maturity, is applicable to industrial application; (4) the three-D nano-porous Graphene that the present invention obtains has self supporting structure, directly can apply without any post-processed, has greatly expanded the Application Areas of Graphene.
Accompanying drawing explanation
Fig. 1 is the photomacrograph of the present invention's alloy foil sheet used;
The nano porous copper SEM image of Fig. 2 prepared by the present invention;
The nanoporous ambrose alloy SEM image of Fig. 3 prepared by the present invention;
The SEM image of Fig. 4 to be the present invention's nano porous copper be three-D nano-porous Graphene prepared by matrix;
The TEM image of Fig. 5 to be the present invention's nano porous copper be three-D nano-porous Graphene prepared by matrix;
The TEM image of Fig. 6 to be the present invention's nanoporous ambrose alloy be three-D nano-porous Graphene prepared by matrix.
Embodiment
The present invention devises a kind of method that nano porous metal prepares three-D nano-porous Graphene, and this preparation method adopts following technique:
1) nano porous metal is prepared
Thickness is selected to be the Cu of 10-200um thickness
30mn
70, Ni
30mn
70, Ni
xcu
30-xmn
70(x=5,10,15,20,25) alloy foil sheet (above ratio is atomic ratio), then intercepts appropriate size, by Cu under room temperature by above alloy foil sheet
30mn
70alloy foil sheet is placed in 0.0125-0.5M hydrochloric acid soln, by Ni
30mn
70, Ni
xcu
30-xmn
70alloy foil sheet is placed in 0.1-5M ammoniumsulphate soln, utilizes chemical process to carry out removal alloying process 30-300 minute; Or above alloy foil sheet is placed in 0.1-5M ammoniumsulphate soln, electrochemical method is utilized to carry out removal alloying process 30-240 minute, corrosion potential is-0.5--0.2V, thus obtains the nano porous metal paillon foil with the nano-porous structure of level with removal alloying time and removal alloying corrosive fluid change in concentration.Obtained nano porous metal paillon foil is first used washed with de-ionized water, then uses washes of absolute alcohol, then for subsequent use by carrying out vacuum-drying 12h under the nano porous metal paillon foil room temperature of cleaning.
2) the many Graphenes of three-dimensional manometer are prepared
The nano porous copper that step 2 is obtained puts into quartz boat, quartz boat is placed in reaction tubes burner hearth external region, pass into carbon source (acetylene, methane or ethene), argon gas and hydrogen, wherein, acetylene, argon gas, hydrogen ratio press the flow configuration of 1-20:500:200; Methane, argon gas, hydrogen ratio press the flow configuration of 10-50:200-500:50-200; Ethene, argon gas, hydrogen ratio press the flow configuration of 1-50:200-500:50-200.Now furnace temperature is risen to 600-1100 DEG C.Rise to after assigned temperature until furnace temperature and quartz boat is quickly moved to flat-temperature zone in the middle part of reaction tubes, calcine 0.5-30 minute at this temperature.After calcining, quartz boat is moved to burner hearth outside from flat-temperature zone in the middle part of reaction tubes fast, and bell is opened, under the atmosphere of argon gas, sample is down to room temperature.Then taken out from tube furnace by sample, immersing proportioning is removed by nano porous metal in the corrosive fluid of 10g iron(ic) chloride+10ml hydrochloric acid+100ml water, and etching time is 12 hours.Subsequently the sample washed with de-ionized water obtained totally can be obtained the three-D nano-porous graphene film of self-supporting.
Embodiment 1
Thickness is selected to be the Cu of 50um
30mn
70alloy foil sheet, and be cut into 1*1cm
2size.Then configuration concentration is the hydrochloric acid soln of 0.05M, alloy foil sheet is immersed in hydrochloric acid soln, at room temperature carry out removal alloying, the removal alloying time is 120 minutes, after removal alloying terminates by paillon foil successively through deionized water-alcohol washes, put into vacuum drying oven after cleaning up, at room temperature vacuum-drying 12 hours, obtains nano porous copper.By drying completely nano porous copper put into quartzy Noah's ark, and Noah's ark is placed in reaction tubes burner hearth external region, pass into acetylene, argon gas and hydrogen, the ratio of three kinds of gases is C
2h
2: Ar:H
2=5:500:200sccm.Meanwhile, tube furnace temperature is risen to 800 DEG C, when furnace temperature arrives 800 DEG C, quartzy Noah's ark is quickly moved to flat-temperature zone in the middle part of reaction tubes from burner hearth outside, react 1 minute at this temperature.Reaction is after reception terminates, and quartz boat moved to burner hearth outside from flat-temperature zone in the middle part of reaction tubes fast, and is opened by bell, close acetylene and hydrogen, under the atmosphere of argon gas, sample is down to room temperature.Then taken out from tube furnace by sample, immersing proportioning is removed by nano porous copper in the corrosive fluid of 10g iron(ic) chloride+10ml hydrochloric acid+100ml water, and etching time is 12 hours.Subsequently the sample washed with de-ionized water obtained totally can be obtained the three-D nano-porous graphene film of self-supporting.
Embodiment 2
Thickness is selected to be the Cu of 150um
30mn
70alloy foil sheet, and be cut into 1*2cm
2size.Then configuration concentration is the ammoniumsulphate soln of 1M, and at room temperature utilize constant potential method alloy to carry out removal alloying, corrosion potential is-0.4V, and etching time is 150 minutes.After removal alloying terminates by paillon foil successively through deionized water-alcohol washes, put into vacuum drying oven after cleaning up, at room temperature vacuum-drying 12 hours, obtains nano porous copper.By drying completely nano porous copper put into quartzy Noah's ark, and Noah's ark is placed in reaction tubes burner hearth external region, pass into methane, argon gas and hydrogen, the ratio of three kinds of gases is C
2h
2: Ar:H
2=20:500:200sccm.Meanwhile, tube furnace temperature is risen to 900 DEG C, when furnace temperature arrives 900 DEG C, quartzy Noah's ark is quickly moved to flat-temperature zone in the middle part of reaction tubes from burner hearth outside, react 0.5 minute at this temperature.Reaction is after reception terminates, and quartz boat moved to burner hearth outside from flat-temperature zone in the middle part of reaction tubes fast, and is opened by bell, close methane and hydrogen, under the atmosphere of argon gas, sample is down to room temperature.Then taken out from tube furnace by sample, immersing proportioning is removed by nano porous copper in the corrosive fluid of 10g iron(ic) chloride+10ml hydrochloric acid+100ml water, and etching time is 12 hours.Subsequently the sample washed with de-ionized water obtained totally can be obtained the three-D nano-porous graphene film of self-supporting.
Embodiment 3
Thickness is selected to be the Ni of 100um
15cu
15mn
70alloy foil sheet, and be cut into 2*1cm
2size.Then configuration concentration is the ammoniumsulphate soln of 1M, and at room temperature utilize constant potential method alloy to carry out removal alloying, corrosion potential is-0.5V, and etching time is 240 minutes.After removal alloying terminates by paillon foil successively through deionized water-alcohol washes, put into vacuum drying oven after cleaning up, at room temperature vacuum-drying 12 hours, obtains nanoporous ambrose alloy.By drying completely nanoporous ambrose alloy put into quartzy Noah's ark, and Noah's ark is placed in reaction tubes burner hearth external region, pass into ethene, argon gas and hydrogen, the ratio of three kinds of gases is C
2h
4: Ar:H
2=1:200:50sccm.Meanwhile, tube furnace temperature is risen to 1000 DEG C, when furnace temperature arrives 1000 DEG C, quartzy Noah's ark is quickly moved to flat-temperature zone in the middle part of reaction tubes from burner hearth outside, react 10 minutes at this temperature.Reaction is after reception terminates, and quartz boat moved to burner hearth outside from flat-temperature zone in the middle part of reaction tubes fast, and is opened by bell, close ethene and hydrogen, under the atmosphere of argon gas, sample is down to room temperature.Then taken out from tube furnace by sample, immersing proportioning is removed by nanoporous ambrose alloy in the corrosive fluid of 10g iron(ic) chloride+10ml hydrochloric acid+100ml water, and etching time is 12 hours.Subsequently the sample washed with de-ionized water obtained totally can be obtained the three-D nano-porous graphene film of self-supporting.
Embodiment 4
Thickness is selected to be the Ni of 100um
30mn
70alloy foil sheet, and be cut into 1*1cm
2size.Then configuration concentration is the ammoniumsulphate soln of 1M, and at room temperature utilize constant potential method alloy to carry out removal alloying, corrosion potential is-0.3V, and etching time is 200 minutes.After removal alloying terminates by paillon foil successively through deionized water-alcohol washes, put into vacuum drying oven after cleaning up, at room temperature vacuum-drying 12 hours, obtains nanoporous nickel.By drying completely nanoporous nickel put into quartzy Noah's ark, and Noah's ark is placed in reaction tubes burner hearth external region, pass into ethene, argon gas and hydrogen, the ratio of three kinds of gases is C
2h
4: Ar:H
2=10:200:200sccm.Meanwhile, tube furnace temperature is risen to 800 DEG C, when furnace temperature arrives 800 DEG C, quartzy Noah's ark is quickly moved to flat-temperature zone in the middle part of reaction tubes from burner hearth outside, react 20 minutes at this temperature.Reaction is after reception terminates, and quartz boat moved to burner hearth outside from flat-temperature zone in the middle part of reaction tubes fast, and is opened by bell, close ethene and hydrogen, under the atmosphere of argon gas, sample is down to room temperature.Then taken out from tube furnace by sample, immersing proportioning is removed by nanoporous nickel in the corrosive fluid of 10g iron(ic) chloride+10ml hydrochloric acid+100ml water, and etching time is 12 hours.Subsequently the sample washed with de-ionized water obtained totally can be obtained the three-D nano-porous graphene film of self-supporting.
Embodiment 5
Thickness is selected to be the Cu of 50um
30mn
70alloy foil sheet, and be cut into 1*1cm
2size.Then configuration concentration is the hydrochloric acid soln of 0.05M, alloy foil sheet is immersed in hydrochloric acid soln, at room temperature carry out removal alloying, the removal alloying time is 30 minutes, after removal alloying terminates by paillon foil successively through deionized water-alcohol washes, put into vacuum drying oven after cleaning up, at room temperature vacuum-drying 12 hours, obtains nano porous copper.By drying completely nano porous copper put into quartzy Noah's ark, and Noah's ark is placed in reaction tubes burner hearth external region, pass into methane, argon gas and hydrogen, the ratio of three kinds of gases is CH
4: Ar:H
2=20:2000:200sccm.Meanwhile, tube furnace temperature is risen to 1000 DEG C, when furnace temperature arrives 1000 DEG C, quartzy Noah's ark is quickly moved to flat-temperature zone in the middle part of reaction tubes from burner hearth outside, react 10 minutes at this temperature.Reaction is after reception terminates, and quartz boat moved to burner hearth outside from flat-temperature zone in the middle part of reaction tubes fast, and is opened by bell, close methane and hydrogen, under the atmosphere of argon gas, sample is down to room temperature.Then taken out from tube furnace by sample, immersing proportioning is removed by nano porous copper in the corrosive fluid of 10g iron(ic) chloride+10ml hydrochloric acid+100ml water, and etching time is 12 hours.Subsequently the sample washed with de-ionized water obtained totally can be obtained the three-D nano-porous graphene film of self-supporting.
Claims (5)
1. a preparation method for three-D nano-porous Graphene, this preparation method adopts following technique:
1) nano porous metal paillon foil is prepared
Thickness is selected to be the Cu of 10-200um
30mn
70, Ni
30mn
70or Ni
xcu
30-xmn
70the alloy foil sheet of (x=5,10,15,20,25), carries out removal alloying process, obtains the nano porous metal paillon foil with the nano-porous structure of level with removal alloying time and removal alloying corrosive fluid change in concentration;
2) the many Graphenes of three-dimensional manometer are prepared
Quartz boat put into by the nano porous metal paillon foil that step 2 is obtained, quartz boat is placed in reaction tubes burner hearth external region, pass into carbon-source gas, argon gas and hydrogen, the ratio of carbon source, argon gas and hydrogen presses the flow configuration of 1-50:200-500:50-200, now furnace temperature is risen to 500-1100 DEG C, rise to after assigned temperature until furnace temperature and quartz boat is quickly moved to flat-temperature zone in the middle part of reaction tubes, calcine 0.5-30 minute at this temperature;
After calcining, quartz boat is moved to burner hearth outside from flat-temperature zone in the middle part of reaction tubes fast, and bell is opened, under the atmosphere of argon gas, sample is down to room temperature; Then sample is taken out from tube furnace, immerse in corrosive fluid and nano porous metal is removed, clean up afterwards and can obtain the three-D nano-porous graphene film of self-supporting.
2. preparation method according to claim 1, is characterized in that, described carbon-source gas is acetylene, methane or ethene.
3. preparation method according to claim 2, is characterized in that, carbon-source gas is acetylene, and acetylene, argon gas, hydrogen ratio press the flow configuration of 1-20:500:200.
4. preparation method according to claim 2, is characterized in that, carbon-source gas is methane, and methane, argon gas, hydrogen ratio press the flow configuration of 10-50:200-500:50-200.
5. preparation method according to claim 2, is characterized in that, carbon-source gas is ethene, and ethene, argon gas, hydrogen ratio press the flow configuration of 1-50:200-500:50-200.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510688992.6A CN105217617A (en) | 2015-10-22 | 2015-10-22 | A kind of preparation method of three-D nano-porous Graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510688992.6A CN105217617A (en) | 2015-10-22 | 2015-10-22 | A kind of preparation method of three-D nano-porous Graphene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105217617A true CN105217617A (en) | 2016-01-06 |
Family
ID=54986973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510688992.6A Pending CN105217617A (en) | 2015-10-22 | 2015-10-22 | A kind of preparation method of three-D nano-porous Graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105217617A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105719852A (en) * | 2016-02-04 | 2016-06-29 | 天津大学 | Preparation method for three-dimensional nano-porous graphene/manganese dioxide composite electrode material |
| CN105887039A (en) * | 2016-05-30 | 2016-08-24 | 天津大学 | Method for directly generating multiporous carbon nanofibers on nanoporous copper |
| CN107416805A (en) * | 2017-04-28 | 2017-12-01 | 北京理工大学 | A kind of method that high conductivity self-supporting graphene film is prepared using plastic waste material |
| CN107416807A (en) * | 2017-08-28 | 2017-12-01 | 天津大学 | A kind of preparation method of the three-D nano-porous graphene of nitrogen oxygen codope |
| CN107502886A (en) * | 2017-07-13 | 2017-12-22 | 天津大学 | The preparation method of fabricated in situ sheet metal hydroxide/oxide composite |
| CN107739869A (en) * | 2017-11-09 | 2018-02-27 | 天津工业大学 | Nanoporous carbon/carbon-copper composite material and preparation method thereof |
| CN107785586A (en) * | 2017-09-19 | 2018-03-09 | 天津大学 | Three-dimensional porous copper/graphene composite current collector for secondary metals cathode of lithium battery |
| CN108242530A (en) * | 2016-12-23 | 2018-07-03 | 北京好风光储能技术有限公司 | A kind of lithium slurry battery and its negative plate |
| WO2018120601A1 (en) * | 2016-12-30 | 2018-07-05 | 天津大学 | Preparation method for self-supporting thin film of graphene-enhanced three-dimensional porous carbon |
| CN108751169A (en) * | 2018-06-08 | 2018-11-06 | 天津大学 | Preparation method for in-situ synthesis of three-dimensional nano-porous graphene-coated metal oxide/hydroxide/sulfide composite material |
| CN108831750A (en) * | 2018-05-24 | 2018-11-16 | 天津大学 | Three-dimensional porous Ni-Co film/CoMoO4The preparation method of composite material |
| CN111254308A (en) * | 2020-01-21 | 2020-06-09 | 天津理工大学 | Method for improving high-temperature stability of metal twin crystal |
| CN113754690A (en) * | 2021-09-02 | 2021-12-07 | 江苏昌吉利新能源科技有限公司 | Preparation method of silyl ether lithium alkyl |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583337A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | Preparation method for graphene material with porous structure |
| CN102674321A (en) * | 2011-03-10 | 2012-09-19 | 中国科学院金属研究所 | Graphene foam with three dimensional fully connected network and macroscopic quantity preparation method thereof |
| CN103738935A (en) * | 2013-12-13 | 2014-04-23 | 天津大学 | Method for preparing porous carbon material by using porous copper as template |
-
2015
- 2015-10-22 CN CN201510688992.6A patent/CN105217617A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674321A (en) * | 2011-03-10 | 2012-09-19 | 中国科学院金属研究所 | Graphene foam with three dimensional fully connected network and macroscopic quantity preparation method thereof |
| CN102583337A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | Preparation method for graphene material with porous structure |
| CN103738935A (en) * | 2013-12-13 | 2014-04-23 | 天津大学 | Method for preparing porous carbon material by using porous copper as template |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105719852A (en) * | 2016-02-04 | 2016-06-29 | 天津大学 | Preparation method for three-dimensional nano-porous graphene/manganese dioxide composite electrode material |
| CN105887039A (en) * | 2016-05-30 | 2016-08-24 | 天津大学 | Method for directly generating multiporous carbon nanofibers on nanoporous copper |
| CN108242530A (en) * | 2016-12-23 | 2018-07-03 | 北京好风光储能技术有限公司 | A kind of lithium slurry battery and its negative plate |
| WO2018120601A1 (en) * | 2016-12-30 | 2018-07-05 | 天津大学 | Preparation method for self-supporting thin film of graphene-enhanced three-dimensional porous carbon |
| CN107416805A (en) * | 2017-04-28 | 2017-12-01 | 北京理工大学 | A kind of method that high conductivity self-supporting graphene film is prepared using plastic waste material |
| CN107502886A (en) * | 2017-07-13 | 2017-12-22 | 天津大学 | The preparation method of fabricated in situ sheet metal hydroxide/oxide composite |
| CN107416807A (en) * | 2017-08-28 | 2017-12-01 | 天津大学 | A kind of preparation method of the three-D nano-porous graphene of nitrogen oxygen codope |
| CN107785586A (en) * | 2017-09-19 | 2018-03-09 | 天津大学 | Three-dimensional porous copper/graphene composite current collector for secondary metals cathode of lithium battery |
| CN107739869A (en) * | 2017-11-09 | 2018-02-27 | 天津工业大学 | Nanoporous carbon/carbon-copper composite material and preparation method thereof |
| CN108831750A (en) * | 2018-05-24 | 2018-11-16 | 天津大学 | Three-dimensional porous Ni-Co film/CoMoO4The preparation method of composite material |
| CN108751169A (en) * | 2018-06-08 | 2018-11-06 | 天津大学 | Preparation method for in-situ synthesis of three-dimensional nano-porous graphene-coated metal oxide/hydroxide/sulfide composite material |
| CN108751169B (en) * | 2018-06-08 | 2021-12-28 | 天津大学 | Preparation method for in-situ synthesis of three-dimensional nano-porous graphene-coated metal oxide/hydroxide/sulfide composite material |
| CN111254308A (en) * | 2020-01-21 | 2020-06-09 | 天津理工大学 | Method for improving high-temperature stability of metal twin crystal |
| CN113754690A (en) * | 2021-09-02 | 2021-12-07 | 江苏昌吉利新能源科技有限公司 | Preparation method of silyl ether lithium alkyl |
| CN113754690B (en) * | 2021-09-02 | 2022-03-25 | 江苏昌吉利新能源科技有限公司 | Preparation method of silyl ether lithium alkyl |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105217617A (en) | A kind of preparation method of three-D nano-porous Graphene | |
| CN105217618A (en) | A kind of preparation method of three-D nano-porous Graphene | |
| Hao et al. | Facile fabrication of core-shell structured Ni (OH) 2/Ni (PO3) 2 composite via one-step electrodeposition for high performance asymmetric supercapacitor | |
| CN105603518B (en) | A kind of method that polycrystalline copper foil is changed into (100) monocrystalline Cu | |
| CN103346299B (en) | Original position etching prepares the method for hollow tin-based oxide/carbon composite nano-material | |
| CN103950923A (en) | New method for preparing high-quality graphene | |
| CN103121670A (en) | Method for low-temperature growth of graphene by remote plasma reinforced atomic layer deposition | |
| CN105719852A (en) | Preparation method for three-dimensional nano-porous graphene/manganese dioxide composite electrode material | |
| CN105006376B (en) | A kind of preparation method of carbon nanotube and nickel oxide composite material | |
| WO2018120601A1 (en) | Preparation method for self-supporting thin film of graphene-enhanced three-dimensional porous carbon | |
| CN111485223A (en) | Boron-doped diamond electrode with ultrahigh specific surface area and preparation method and application thereof | |
| CN107644743A (en) | A kind of preparation method of the three-dimensional porous nitrogen-doped graphene of self-supporting-nickel hydroxide electrochemical capacitance electrode material | |
| CN105063571A (en) | Preparation method for three-dimensional graphene on stainless steel substrate | |
| CN106219525A (en) | A kind of preparation method of expanded graphite paper | |
| CN104150470A (en) | Metal-solution reduction method for preparing graphene | |
| CN110143616A (en) | A kind of preparation method of the rhenium disulfide nanometer sheet of vertical-growth | |
| Lv et al. | Investigation of microstructures of ZnCo2O4 on bare Ni foam and Ni foam coated with graphene and their supercapacitors performance | |
| CN103345979A (en) | Method for manufacturing graphene conductive thin film | |
| CN105845463A (en) | Method for preparing combined electrode material based on three-dimensional graphene /nickel hydroxide | |
| CN103626117A (en) | Method for preparing tungsten oxide nanowire/porous silicon composite structure material at low temperature | |
| CN107502886A (en) | The preparation method of fabricated in situ sheet metal hydroxide/oxide composite | |
| CN107151009B (en) | A kind of nitrogen-doped graphene and its preparation method and application | |
| CN107570176B (en) | Porous single-layer MoS1.85Preparation method and application of nano-net | |
| Ning et al. | High-quality graphene grown directly on stainless steel meshes through CVD process for enhanced current collectors of supercapacitors | |
| Zhou et al. | Controllable preparation of vertically standing graphene sheets and their wettability and supercapacitive properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160106 |
|
| WD01 | Invention patent application deemed withdrawn after publication |