CN103236528A - Germanium-carbon-graphene composite material, and preparation method and application thereof - Google Patents
Germanium-carbon-graphene composite material, and preparation method and application thereof Download PDFInfo
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- CN103236528A CN103236528A CN2013101407773A CN201310140777A CN103236528A CN 103236528 A CN103236528 A CN 103236528A CN 2013101407773 A CN2013101407773 A CN 2013101407773A CN 201310140777 A CN201310140777 A CN 201310140777A CN 103236528 A CN103236528 A CN 103236528A
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- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 29
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 229940119177 germanium dioxide Drugs 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 36
- 239000010439 graphite Substances 0.000 claims description 36
- -1 germanium carbon graphite alkene Chemical class 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 16
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 9
- KCFIHQSTJSCCBR-UHFFFAOYSA-N [C].[Ge] Chemical compound [C].[Ge] KCFIHQSTJSCCBR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims 4
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 239000011257 shell material Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a germanium-carbon-graphene composite material which is compounded from nano germanium. germanium dioxide, flocculent carbon and reduction-oxidation graphene, wherein the germanium dioxide is coated on the surface layer of the germanium to form a core shell, thereby forming nano core-shell particles; and the nano core-shell particles are uniformly dispersed and distributed in the flocculent carbon, and coated by the reduction-oxidation graphene network. The invention also discloses a preparation method and application of the germanium-carbon-graphene composite material. The germanium-carbon-graphene composite material disclosed by the invention has the characteristics of high capacity, high ratio and high loop stability, and has the advantages of simple preparation technique, low energy consumption, high yield and no pollution.
Description
Technical field
The present invention relates to lithium ion battery negative material, particularly a kind of germanium carbon graphite alkene composite material and its preparation method and application.
Background technology
Lithium ion battery has the important strategic meaning at new energy field, is the hot spot technology that current generation economic development and government support.The selection of negative material system and performance thereof are one of key factors that determines lithium ion battery performance of new generation.The capacity of traditional business-like carbon negative pole material reaches capacity, and the problem of its essence is the low (372mAhg of the theoretical capacity of material with carbon element
-1).In numerous non-carbon negative pole material systems after deliberation, metal Ge system is as lithium ion battery negative material capacity height not only, and the lithium ion diffusion coefficient is big, be 400 times of Si, good conductivity can satisfy at present for high power capacity, high magnification, eco-friendly lithium ion battery growth requirement.But because embedding lithium and take off the bigger change in volume of existences in the lithium process, and efflorescence gradually breaks away from collector and causes the active material inefficacy.For overcoming this obstacle, can adopt nanometer reduce size (nano wire, nanotube, film etc.), doping inert matter with fixedly active material, carbon coated shell or admixed graphite alkene with strategies such as buffer volumes expansions.In numerous strategies, simple nanometer or alloying effect are not remarkable and cost is higher, are not suitable for industrial applications.And have high conductivity and better the carbonaceous material of ductility be to cushion the volumetric expansion of Metal Substrate active material and the best method of improving its cycle performance.Particularly have high conductivity, bigger serface, outstanding heat and the Graphene of chemical stability and favorable mechanical performance, more can be effectively as the decompression pad of germanium base negative material in the charge and discharge process change in volume, and can keep the high conductance of entire electrode and lithium ion diffusion rate, when making germanium base lithium ion cell negative electrode material keep high power capacity, can significantly improve circulation and high rate performance again.
Summary of the invention
Above-mentioned shortcoming and deficiency in order to overcome prior art the object of the present invention is to provide a kind of germanium carbon graphite alkene composite material (Ge@GeO
2@C/RGO, wherein @ represents that shell coats, and/expression mixes mutually, and Ge represents germanium particle, GeO
2The expression germanium dioxide, C represents the carbon phase, RGO represents redox graphene), taken into account high power capacity, high magnification and high cyclical stability characteristics.
Another object of the present invention is to provide the preparation method of above-mentioned germanium carbon graphite alkene composite material, germanium carbon proportion speed is easily weighed, and step is simple, easily realizes suitability for industrialized production.
A further object of the present invention is to provide the application of above-mentioned germanium carbon graphite alkene composite material.
Purpose of the present invention is achieved through the following technical solutions:
A kind of germanium carbon graphite alkene composite material is composited by nano level germanium, germanium dioxide, cotton-shaped carbon and the redox graphene (RGO) of group, and wherein, the top layer that germanium dioxide is coated on germanium forms nucleocapsid, and germanium and germanium dioxide form the nano core-shell particle; The ground disperse of described nano core-shell uniform particles is distributed in the cotton-shaped carbon of group, and is reduced the graphene oxide network and coats.
A kind of preparation method of germanium carbon graphite alkene composite material may further comprise the steps:
(1) adopts high energy pendulum shake ball mill (QC-3M) under oxidizing atmosphere, pure germanium raw material and graphite raw material to be carried out ball milling, obtain Ge@GeO
2The @C composite material; Described Ge@GeO
2The @C composite material by the nanometer germanium uniform particles disperse with germanium dioxide shell form in the cotton-shaped carbon of the group of being distributed in;
(2) with Ge@GeO
2The @C composite material carries out ultrasonic the mixing in alcoholic solution with redox graphene, obtains germanium carbon graphite alkene composite material after vacuumize, i.e. Ge@GeO
2The @C/RGO composite material.
The mass ratio of described pure germanium raw material and graphite raw material is 1:0.1～1.
Described Ge@GeO
2The mass ratio of @C composite material and redox graphene is 1:0.1～0.8.
The time of described ball milling is 4～10h.
The preparation method of described redox graphene is as follows: adopt improvement Hummers method to prepare graphite oxide, obtain redox graphene with hydrazine hydrate reduction.
Described germanium carbon graphite alkene composite material Ge@GeO
2@C/RGO is as lithium ion battery negative material.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) Ge@GeO of the present invention's preparation
2The @C/RGO composite material has the three-layer protection structure, as lithium ion battery negative material the time, and the similar structures that chemical relatively legal system is equipped with, the Li that the oxide shell that has more and Li reaction back form
2O plays fixedly nanometer germanium particle, prevents from reuniting and as the first line of defence of change in volume in the germanium charge and discharge process, the redox graphene network of the cotton-shaped carbon-coating of the group that forms behind the high-energy ball milling and mixing is respectively as second road and the 3rd road shell.The germanium carbon graphite alkene composite material of the present invention's preparation has been taken into account high power capacity, high magnification and good cyclical stability characteristics.
(2) Ge@GeO of the present invention's preparation
2The preparation process technology of @C/RGO composite material is simple, and power consumption is few, output height, pollution-free.
(3) Ge@GeO of the present invention's preparation
2The @C/RGO composite material not only can satisfy lithium ion battery instantly to the requirement of high-energy-density high magnification development, more can expand for other matrix negative materials.
Description of drawings
Fig. 1 is the germanium carbon composite construction Ge@GeO of embodiments of the invention 1 preparation
2The SEM figure of @C.
Fig. 2 is the SEM figure of the redox graphene RGO of embodiments of the invention 1 preparation.
Fig. 3 is the germanium carbon of embodiments of the invention 1 preparation and the Ge@GeO that the compound back of redox graphene forms
2The XRD spectra of @C/RGO composite material.
Fig. 4 is the Ge@GeO of embodiments of the invention 1 preparation
2The SEM figure of @C/RGO composite material.
Fig. 5 is the Ge@GeO of embodiments of the invention 1 preparation
2The cycle performance curve chart of @C/RGO composite material.
Fig. 6 is the Ge@GeO of embodiments of the invention 2 preparations
2The SEM figure of @C/RGO composite material.
Fig. 7 is the Ge@GeO of embodiments of the invention 3 preparations
2The cycle performance curve chart of @C/RGO condensation material.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The preparation method of the germanium carbon graphite alkene composite material of present embodiment may further comprise the steps:
(1) adopt high energy pendulum shake ball mill (QC-3M) under oxidizing atmosphere pure germanium raw material and graphite raw material to be carried out ball milling, germanium forms micro-germanium dioxide shell on its surface in the nanometer process, and wherein the mass ratio of pure germanium raw material and graphite raw material is 1:1; Abrading-ball and raw meal mass ratio are 20:1, and the ball milling time is 10h, the Ge@GeO that obtains
2The @C composite material, its surface topography is as shown in Figure 1;
(2) adopt improvement Hummers method to prepare graphite oxide, obtain redox graphene with hydrazine hydrate reduction, its surface topography as shown in Figure 2;
(3) with the germanium carbon complex nucleus shell material Ge@GeO for preparing behind the ball milling
2@C carries out ultrasonic the mixing in alcoholic solution by mass ratio 1:0.1 with redox graphene, obtains germanium carbon graphite alkene composite material Ge@GeO after the slow drying of vacuum
2@C/RGO:, its XRD spectra as shown in Figure 3, surface topography is as shown in Figure 4.
Fig. 1～4 are the Ge@GeO of present embodiment preparation as can be known
2The @C/RGO composite material is composited by nano level germanium, germanium dioxide, cotton-shaped carbon and the redox graphene of group, and wherein, the top layer that germanium dioxide is coated on germanium forms nucleocapsid, and germanium and germanium dioxide form the nano core-shell particle; The ground disperse of described nano core-shell uniform particles is distributed in the cotton-shaped carbon of group, and is reduced the graphene oxide network and coats.
Below to the Ge@GeO of present embodiment preparation
2The @C/RGO performance of composites is tested:
The Ge@GeO that drying is good
2@C/RGO composite powder, conductive agent super-p and binding agent Pvdf mix to be coated on by mass ratio 8:1:1 and are made into electrode slice on the Copper Foil.In the argon gas atmosphere glove box, with lithium metal as to electrode, ethylene carbonate (EC)+dimethyl carbonate (DMC)+1MLiPF
6Be electrolyte, be assembled into button cell and test.Test condition is: charging and discharging currents density is 200mA/g and 1000mA/g, and discharging and recharging by voltage is 0.01V～1.5V (vs.Li
+/ Li).
Fig. 5 is the Ge@GeO of present embodiment preparation
2@C/RGO composite material cycle performance curve is (with Ge@GeO
2@C:RGO1:0.1wt%, ball milling time 10h, discharge-rate 0.2C are example), as can be known, the Ge@GeO of present embodiment preparation
2The discharge capacity first of @C/RGO composite material is 2665mAhg
-1, 50 times circulation back discharge capacity is 875mAhg
-1
Embodiment 2
The preparation method of the germanium carbon graphite alkene composite material of present embodiment, the mass ratio that removes pure germanium raw material and graphite raw material is 1:0.1, Ge@GeO
2The mass ratio of @C composite material and redox graphene is outside the 1:0.8, and all the other features and embodiment 1 are together.
The Ge@GeO of present embodiment preparation
2The surface topography of @C/RGO composite material as shown in Figure 6.
Under 2C charge-discharge magnification condition, carry out charge-discharge test after the germanium carbon graphite alkene composite material of present embodiment preparation made lithium ion battery negative electrode slice and assembled battery.The Ge@GeO of preparation
2The @C/RGO composite material its first discharge capacity be 1060mAhg
-1, capacity remains on 413mAhg after 100 circulations
-1
Embodiment 3
The preparation method of the germanium carbon graphite alkene composite material of present embodiment, except the mass ratio of pure germanium raw material and graphite raw material is that 1:0.5, ball milling time are the 4h, all the other features and embodiment 1 with.
Under 2C charge-discharge magnification condition, carry out charge-discharge test after the germanium carbon graphite alkene composite material of present embodiment preparation made lithium ion battery negative electrode slice and assembled battery, multiplying power cycle performance curve as shown in Figure 7, discharge capacity is 1841mAhg first as can be known
-1, 100 times circulation back capacity remains on 575mAhg
-1
Above-described embodiment is preferred implementation of the present invention; but embodiments of the present invention are not limited by the examples; other any do not deviate from change, the modification done under spiritual essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. germanium carbon graphite alkene composite material, it is characterized in that, be composited by nano level germanium, germanium dioxide, cotton-shaped carbon and the redox graphene of group, wherein, the top layer that germanium dioxide is coated on germanium forms nucleocapsid, and germanium and germanium dioxide form the nano core-shell particle; The ground disperse of described nano core-shell uniform particles is distributed in the cotton-shaped carbon of group, and is reduced the graphene oxide network and coats.
2. the preparation method of a germanium carbon graphite alkene composite material is characterized in that, may further comprise the steps:
(1) adopts high energy pendulum shake ball mill under oxidizing atmosphere, pure germanium raw material and graphite raw material to be carried out ball milling, obtain Ge@GeO
2The @C composite material; Described Ge@GeO
2The @C composite material by the nanometer germanium uniform particles disperse with germanium dioxide shell form in the cotton-shaped carbon of the group of being distributed in;
(2) with Ge@GeO
2The @C composite material carries out ultrasonic the mixing in alcoholic solution with redox graphene, obtains germanium carbon graphite alkene composite material after vacuumize.
3. the preparation method of the described germanium carbon graphite of claim 2 alkene composite material is characterized in that, the mass ratio of described pure germanium raw material and graphite raw material is 1:0.1～1.
4. the preparation method of the described germanium carbon graphite of claim 2 alkene composite material is characterized in that described Ge@GeO
2The mass ratio of @C composite material and redox graphene is 1:0.1～0.8.
5. the preparation method of claim 2 or 3 described germanium carbon graphite alkene composite materials is characterized in that the time of described ball milling is 4～10h.
6. the preparation method of the described germanium carbon graphite of claim 2 alkene composite material is characterized in that the preparation method of described redox graphene is as follows: adopt improvement Hummers method to prepare graphite oxide, obtain redox graphene with hydrazine hydrate reduction.
7. the described germanium carbon graphite of claim 1 alkene composite material is as lithium ion battery negative material.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466104A (en) * | 2014-11-19 | 2015-03-25 | 东莞市翔丰华电池材料有限公司 | Germanium-graphene composite cathode material for lithium ion battery and preparation method thereof |
| CN104659346A (en) * | 2015-02-11 | 2015-05-27 | 深圳新宙邦科技股份有限公司 | Germanium/carbon composite negative electrode material and preparation method thereof |
| CN104733719A (en) * | 2013-12-24 | 2015-06-24 | 中国电子科技集团公司第十八研究所 | Method for preparing germanium-based cathode material for lithium ion battery by adopting carbothermic reduction method |
| CN104733707A (en) * | 2013-12-24 | 2015-06-24 | 中国电子科技集团公司第十八研究所 | Preparation method of germanium-based cathode material for lithium ion battery |
| CN105006551A (en) * | 2015-06-03 | 2015-10-28 | 中南大学 | Stannic phosphide/graphene composite cathode material for sodium-ion battery and preparation method thereof |
| CN108281627A (en) * | 2018-01-03 | 2018-07-13 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery germanium carbon compound cathode materials and preparation method thereof |
| CN111540745A (en) * | 2020-05-13 | 2020-08-14 | 复旦大学 | Low-power-consumption two-dimensional material semi-floating gate memory and preparation method thereof |
| CN111640927A (en) * | 2020-06-17 | 2020-09-08 | 中国人民解放军国防科技大学 | Graphene-bridged polythiophene-coated germanium nanoparticle composite material and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104733719A (en) * | 2013-12-24 | 2015-06-24 | 中国电子科技集团公司第十八研究所 | Method for preparing germanium-based cathode material for lithium ion battery by adopting carbothermic reduction method |
| CN104733707A (en) * | 2013-12-24 | 2015-06-24 | 中国电子科技集团公司第十八研究所 | Preparation method of germanium-based cathode material for lithium ion battery |
| CN104466104A (en) * | 2014-11-19 | 2015-03-25 | 东莞市翔丰华电池材料有限公司 | Germanium-graphene composite cathode material for lithium ion battery and preparation method thereof |
| CN104659346A (en) * | 2015-02-11 | 2015-05-27 | 深圳新宙邦科技股份有限公司 | Germanium/carbon composite negative electrode material and preparation method thereof |
| CN105006551A (en) * | 2015-06-03 | 2015-10-28 | 中南大学 | Stannic phosphide/graphene composite cathode material for sodium-ion battery and preparation method thereof |
| CN105006551B (en) * | 2015-06-03 | 2017-06-06 | 中南大学 | A kind of sodium-ion battery phosphorization tin/Graphene anode material and preparation method thereof |
| CN108281627A (en) * | 2018-01-03 | 2018-07-13 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery germanium carbon compound cathode materials and preparation method thereof |
| CN111540745A (en) * | 2020-05-13 | 2020-08-14 | 复旦大学 | Low-power-consumption two-dimensional material semi-floating gate memory and preparation method thereof |
| CN111640927A (en) * | 2020-06-17 | 2020-09-08 | 中国人民解放军国防科技大学 | Graphene-bridged polythiophene-coated germanium nanoparticle composite material and preparation method and application thereof |
| CN111640927B (en) * | 2020-06-17 | 2021-10-01 | 中国人民解放军国防科技大学 | Graphene-bridged polythiophene-coated germanium nanoparticle composite material and preparation method and application thereof |
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| CN103236528B (en) | 2016-01-20 |
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