CN102956899B - A kind of method of graphite felt electrode phosphorus doping used for all-vanadium redox flow battery - Google Patents
A kind of method of graphite felt electrode phosphorus doping used for all-vanadium redox flow battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 88
- 239000010439 graphite Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 45
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 22
- 239000011574 phosphorus Substances 0.000 title claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 8
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 238000005520 cutting process Methods 0.000 claims abstract description 4
- 238000004544 sputter deposition Methods 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- -1 phosphorus compound Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 description 18
- 230000004048 modification Effects 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention relates to a kind of method of graphite felt electrode phosphorus doping used for all-vanadium redox flow battery, adopt Ultrasonic Cleaning graphite felt, the graphite felt clean through Ultrasonic Cleaning is dried, by putting into reative cell after given size cutting as matrix (or substrate), reative cell is vacuumized, the inert gas containing P elements is passed into certain flow in reaction, adopt Linear ion beam source device or enclosed electronic cyclotron resonance plasma sputter equipment, by sputtering in phosphorous atmosphere, graphite felt is processed, thus increase the graphite felt phosphorous number of functional groups in surface and phosphorus element content.Advantage of the present invention is, novel, method environmental protection.The impurity on graphite felt surface can be removed on the one hand, increase the content of graphite felt surface P elements, improve the chemical property of graphite felt.Improve the systematicness of material with carbon element on the other hand, promote the cyclization process of graphite felt materials simultaneously, increase the micropore quantity of graphite felt.
Description
Technical field
The present invention relates to the processing method of the graphite felt electrode in all-vanadium flow battery field, particularly a kind of method of graphite felt electrode phosphorus doping used for all-vanadium redox flow battery.
Background technology
In recent years, along with going deep into of studying material with carbon element, it is found that at material with carbon element body middle introducing oxygen, nitrogen, sulphur and phosphorus etc. mutually, the chemical property of material with carbon element, mechanical performance, optical property can be improved.And the foreign atoms such as oxygen, nitrogen, sulphur and phosphorus are introduced at carbon material surface, can significantly increase carbon material surface activity, make it in adsorption process of electric transmission flow and reaction medium etc., all show better performance, and then become the study hotspot of electrochemical cell electrode material.
The all-vanadium flow battery of present application adopts graphite felt as battery electrode usually.According to the knowledge of the applicant, graphite felt is not strong due to electro-chemical activity, needs to strengthen its electro-chemical activity by the method for modification.The method of conventional graphite felt modification, has air oxidation process, strong acid oxidizing process and ammoniation process etc.
Wherein, air oxidation process easily causes graphite felt surface etch; The corrosion of strong acid oxidizing process to graphite felt surface is even more serious, the technical method that document " chemical modification of graphite felt electrode and the electrochemical behavior in acid vanadium solution thereof " as being published in August, 2005 on China YouSe Acta Metallurgica Sinica is introduced, adopt the embody rule that strong acid oxidizing process processes graphite felt exactly, applicant finds through research, this technical method is applied to suitability for industrialized production, environmental requirement is high, and carbon fiber surface vigorous reaction can be caused, make fiber surface occur corrosion, the consequence reducing the materials'use life-span can be caused; And it is very tight to reaction condition requirement to adopt ammoniation process to carry out modification to graphite felt, a kind of ammoniated treatment method that master's thesis " all-vanadium flow battery graphite felt electrode study on the modification " of such as Central South University in 2011 is introduced is exactly like this, the method uses reactor to carry out ammoniated treatment to graphite felt, but after process, the nitrogen element content of graphite felt is not high, and reaction condition is very harsh.
At present, the research of mixing phosphorus in material with carbon element is less, one-step method is adopted to prepare thermosetting phenolic resin during the document being published in battery magazine in August, 2000 " mixes the preparation of phosphorus material with carbon element and embedding lithium behavior thereof ", determine suitable carburizing temperature by charge-discharge test, and then prepare the doping phenolic resins pyrolysis carbon of different phosphorus content.Result shows that the ordering degree of material with carbon element improves, and surface activity strengthens, and improves the embedding lithium ability of lithium battery.Wherein, phosphorus is mainly connected with carbocyclic ring with covalent bond, but the method belongs to body mixes, and if the method for graphite felt, modify to the preparation technology of graphite felt, the production process of graphite felt can be increased, reduce the production efficiency of graphite felt.
Chinese patent literature CN101182678A(number of patent application 200710202374.1) disclosed " graphite felt surface modifying method and modified graphite felt " provide a kind of modification processing method that simultaneously can improve graphite felt wettability and electro-chemical activity.The method adopts electrochemical cathode modification to combine to graphite felt electrode modifying surface with traditional Anodic modification, and its wettability and electro-chemical activity are improved, thus improves voltage efficiency and discharge performance in battery charge and discharge process.The graphite felt surface modifying treatment provided: first carry out electrochemical cathode modification before anodic oxidation modification.Further, comprise the following steps: the process of a. electrochemical cathode: take graphite felt as negative electrode, alkali lye is electrolyte, pass into direct current and electrochemical cathode modification is carried out to graphite felt, then with the alkali lye on distilled water cleaning graphite felt surface; B. electrochemical anodic oxidation modification: cleaned clean graphite felt is made anode, with the sulfuric acid solution of 0.05 ~ 4M for electrolyte, passes into direct current and carries out anodic oxidation modification to graphite felt.Need to clean the acid on its surface according to actual conditions needs and subsequent treatment, in order to clean more fast, totally wherein, the temperature passed in a step when direct current carries out electrochemical cathode modification to graphite felt is 50 ~ 90 DEG C, and current density is 75 ~ 160mA/cm
2, the processing time is 4 ~ l0min.Electrolyte described in a step is at least one in the strong base solution of alkali metal salt soln, 10 ~ 40g/l.Electrolyte can be selected: at least one in the sodium phosphate of the NaOH of 10 ~ 40g/l, the sodium carbonate of 0.1 ~ 20g/1,0.1 ~ 20g/1.The concrete kind that electrolyte adds and consumption, can carry out adjustment according to the needs of basicity and determine.In order to effectively process the larger graphite felt of lipophile, emulsifying agent 1 ~ 2g/l can be added in electrolyte described in a step.Mentioned emulsifier is preferably at least one in soap, odium stearate, lauryl sodium sulfate.Wherein, in b step, the concentration of sulfuric acid solution is preferably 1M.Modified graphite felt substantially improves electro-chemical activity as electrode in for the preparation of vanadium redox battery, improve the voltage efficiency of battery discharge, the efficiency of the energy content of battery, improve its stable discharging time simultaneously, thus the charge-discharge performance of vanadium redox battery is greatly improved; And the method operation is simple, do not need special installation, with low cost.It is carry out electrochemical cathode modification before anodic oxidation modification to the modification of graphite felt, but it uses NaOH and this kind of chemical substance with severe corrosive of sulfuric acid.When the sodium phosphate wherein used is as electrolyte, be that anode modification is carried out to graphite felt, increase the oxy radical quantity on graphite felt surface, instead of for increasing phosphorus element content in graphite felt surface.
Summary of the invention
The object of the invention is, for above-mentioned prior art Problems existing, propose and study a kind of method of graphite felt electrode phosphorus doping used for all-vanadium redox flow battery.The method environmental protection, is convenient to implement.The method, to graphite felt electrode surface modification, directly enhances the phosphorous number of functional groups in graphite felt surface participating in reaction, can effective controlled doping degree, and efficiency is high, and does not damage machinery and the chemical property of graphite felt.
Technical solution of the present invention is, adopt Ultrasonic Cleaning graphite felt, it is characterized in that, the graphite felt clean through Ultrasonic Cleaning is dried, by putting into reative cell after given size cutting as matrix or substrate, reative cell is vacuumized, the inert gas containing P elements is passed in reaction, adopt Linear ion beam source device or enclosed electronic cyclotron resonance plasma sputter equipment, by sputtering in phosphorous atmosphere, graphite felt is processed, thus increase the graphite felt phosphorous number of functional groups in surface and phosphorus element content.
It is characterized in that, the inert gas containing P elements passed in reaction is the argon gas containing part phosphorus compound.
It is characterized in that, adjusting reaction flow and reaction time by changing the flow of inert gas containing P elements and flow-rate ratio, reaction time, the voltage of instrument or current parameters.
It is characterized in that, reative cell vacuumizes rear air pressure need be less than 5 × 10
-5handkerchief, the flow velocity passing into the inert gas containing P elements is 10ml/min ~ 100ml/min.
It is characterized in that, the operating current of Linear ion beam source device is set to 0.1A ~ 0.5A, and operating voltage controls at 1400V ± 50V, and workpiece negative pressure is-100V ~-200V, and the operating time is 10min ~ 600min.
It is characterized in that, adopt enclosed electronic cyclotron resonance plasma sputter equipment, to put into the graphite felt of reative cell as substrate process time, substrate adopts floating potential, or adds the bias voltage of-120V ~+120V.
Innovative point of the present invention is: 1, adopt Linear ion beam source device or enclosed electronic cyclotron resonance plasma sputter equipment to process graphite felt.2, use the present invention to carry out phosphorating treatment to graphite felt, the phosphorus element content on graphite felt surface can be increased.3, the present invention can remove the impurity such as the amorphous carbon on graphite felt surface, and does not cause damage to graphite felt surface, thus effectively improves the chemism of graphite felt.
Advantage of the present invention is, novel, method environmental protection.The present invention processes graphite felt electrode, can remove the impurity on graphite felt surface on the one hand, increases the content of graphite felt surface P elements, improves the chemical property of graphite felt.The phosphorus of doping can enter in the carbon-coating space of graphite felt on the other hand, and improve the systematicness of material with carbon element, promote the cyclization process of graphite felt materials simultaneously, wetability and the electro-chemical activity of graphite felt can improve in phosphorous functional group, and increase the micropore quantity of graphite felt.
Embodiment
Below, embodiments of the invention are described in detail:
The present invention adopts Ultrasonic Cleaning graphite felt, the graphite felt clean through Ultrasonic Cleaning is dried, by putting into reative cell after given size cutting as matrix or substrate, reative cell is vacuumized, the inert gas containing P elements is passed into certain flow in reaction, adopting Linear ion beam source device or enclosed electronic cyclotron resonance plasma sputter equipment, by sputtering in phosphorous atmosphere, graphite felt being processed, thus increase the graphite felt phosphorous number of functional groups in surface and phosphorus element content.
Embodiment 1:
(1) graphite felt is put into deionized water, ultrasonic 15min, dry, then use deionized water rinsing, dry for standby.
(2) graphite felt being cut into suitable size is put into reative cell as matrix, vacuumized by reative cell, reative cell vacuumizes rear air pressure need be less than 5 × 10
-5handkerchief, pass into the argon gas (a kind of inert gas) containing 10% hydrogen phosphide with the speed of 30ml/min during reaction, the flow velocity passing into the inert gas containing P elements is 10ml/min ~ 100ml/min.The method adopting Linear ion beam source device to be sputtered by (linear ion bundle mixing magnetic control) is processed graphite felt surface.Wherein, the operating current of Linear ion beam source device is set to 0.2A, and operating voltage controls at 1400V ± 50V, and workpiece negative pressure is-200V, and the reaction time is 50min.
(3) distilled water is used to clean treated graphite felt, dry 12h in 120 DEG C of baking ovens.
The graphite felt using the present invention to obtain is as the electrode fabrication material of vanadium cell.
Embodiment 2:
(1) graphite felt is put into deionized water, ultrasonic 15min, dry, then use deionized water rinsing, dry for standby.
(2) graphite felt being cut into suitable size is put into reative cell as substrate, vacuumized by reative cell, reative cell vacuumizes rear air pressure need be less than 5 × 10
-5handkerchief, pass into the argon gas (a kind of inert gas) containing 10% hydrogen phosphide with the speed of 30ml/min during reaction, the flow velocity passing into the inert gas containing P elements is 10ml/min ~ 100ml/min.Adopt enclosed electronic cyclotron resonance plasma sputter equipment, the method sputtered by (enclosed electronic cyclotron resonance plasma) is processed graphite felt surface, and the reaction time is 200min.
Before process, the vacuum degree of reative cell is 2 × 10
-6pa, vacuum degree when reacting after insufflation gas is 2 × 10
-2pa.
(3) distilled water is used to clean treated graphite felt, dry 12h in 120 DEG C of baking ovens.
Adopt enclosed electronic cyclotron resonance plasma sputter equipment, to put into the graphite felt of reative cell as substrate process time, substrate can be floating potential, also can add the bias voltage of-120V ~+120V.
The graphite felt using the present invention to obtain is as the electrode fabrication material of vanadium cell.
Claims (2)
1. the method for a graphite felt electrode phosphorus doping used for all-vanadium redox flow battery, adopt Ultrasonic Cleaning graphite felt, the graphite felt clean through Ultrasonic Cleaning is dried, by putting into reative cell after given size cutting as matrix or substrate, reative cell is vacuumized, it is characterized in that, the inert gas containing P elements is passed into certain flow in reaction, adopt Linear ion beam source device or enclosed electronic cyclotron resonance plasma sputter equipment, by sputtering in phosphorous atmosphere, graphite felt is processed, thus increase the graphite felt phosphorous number of functional groups in surface and phosphorus element content, the inert gas containing P elements passed into certain flow in reaction is the argon gas containing part phosphorus compound, reaction flow and time is adjusted by changing the flow of inert gas containing P elements and flow-rate ratio, reaction time, the voltage of instrument or current parameters, reative cell vacuumizes rear air pressure need be less than 5 × 10
-5handkerchief, the flow velocity passing into the inert gas containing P elements is 10ml/min ~ 100ml/min, the operating current of Linear ion beam source device is set to 0.1A ~ 0.5A, and operating voltage controls at 1400V ± 50V, and workpiece negative film pressure is-100V ~-200V, and the operating time is 10min ~ 600min.
2. the method for a kind of graphite felt electrode phosphorus doping used for all-vanadium redox flow battery according to claim 1, it is characterized in that: for enclosed electronic cyclotron resonance plasma sputter equipment, substrate can be floating potential, also can add the bias voltage of-120V ~+120V.
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| CN106654235B (en) * | 2017-02-08 | 2020-01-24 | 深圳市贝特瑞新能源材料股份有限公司 | Composite graphite material, preparation method thereof and lithium ion battery containing composite graphite material |
| CN108539210A (en) * | 2017-03-03 | 2018-09-14 | 湖南省银峰新能源有限公司 | Heteroatom doping flow battery electrode material |
| CN109216709A (en) * | 2017-06-29 | 2019-01-15 | 中国科学院金属研究所 | A kind of dig pit effect construction method and its application of high-ratio surface carbon fiber felt |
| CN108365229A (en) * | 2018-02-08 | 2018-08-03 | 成都理工大学 | A kind of bigger serface N doping carbon cloth electrode and preparation method thereof, application |
| CN110534757A (en) * | 2019-09-11 | 2019-12-03 | 上海交通大学 | High performance carbon electrode and preparation method thereof |
| JP2022551449A (en) * | 2019-10-09 | 2022-12-09 | エリコン サーフェス ソリューションズ アーゲー、 プフェフィコン | Method for Producing Corrosion and Wear Resistant Cast Iron Brake Discs |
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| 磷掺杂类金刚石薄膜的制备与性能研究;王进等;《真空科学与技术学报》;20050430;第25卷(第2期);全文 * |
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