CN101923907B - Calcium carbonate/nickel composite conductive powder and preparation method thereof - Google Patents
Calcium carbonate/nickel composite conductive powder and preparation method thereof Download PDFInfo
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- CN101923907B CN101923907B CN2010102557609A CN201010255760A CN101923907B CN 101923907 B CN101923907 B CN 101923907B CN 2010102557609 A CN2010102557609 A CN 2010102557609A CN 201010255760 A CN201010255760 A CN 201010255760A CN 101923907 B CN101923907 B CN 101923907B
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 122
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 61
- 239000000843 powder Substances 0.000 title claims abstract description 56
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 18
- 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 17
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000012423 maintenance Methods 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000005357 flat glass Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002216 antistatic agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 11
- 229910001453 nickel ion Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000007812 deficiency Effects 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000080590 Niso Species 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000035899 viability Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a calcium carbonate/nickel composite conductive powder and a preparation method thereof. The calcium carbonate/nickel composite conductive powder is prepared by a method of performing in-situ reduction on the surface of a calcium carbonate nano-assembled sphere. The method comprises the following steps of: putting the corresponding calcium carbonate nano-assembled sphere and a nickel source into a reactor, taking water as a medium, adding a proper amount of coupling agent, and adjusting the temperature and a pH value of the system to make the system perform the in-situ reduction; and after full reaction, performing the treatment processes such as filtering, washing, drying and the like on the obtained product to prepare the calcium carbonate/nickel composite conductive powder. The prepared conductive powder has the advantages of high dispersibility, small particle size, uniform size distribution, excellent conductivity, high chemical stability and the like, and can be widely applied to the fields of antistatic materials, anticorona coatings and the like.
Description
Technical field
The invention belongs to domain of inorganic chemistry, be specifically related to a kind of calcium carbonate/nickel composite conductive powder and preparation method thereof.
Background technology
In recent years, along with the continuous progress of society's science and technology, people also progressively improve the requirement of conducting function material.Conductive powder body is as a kind of important conducting function material, multiple fields such as the oil that is widely used, chemical industry, communication, electronics, automobile and pottery.Traditional conductive powder body commonly used has carbon system (carbon black, graphite, acetylene black and carbon fiber etc.), metal system (metal-powder and metallic fiber etc.) and burning system (ATO and ZAO etc.).The major defect of carbon series conductive powder is that bad dispersibility, tone are single, production and use are prone to stain operational environment; Metal is many deficiencies such as the conductive powder body existence costs an arm and a leg, and production cost is high, and weatherability is not good; And burning system powder is because poor electric conductivity, is prone to precipitated and separated takes place and comparatively rare in practical application.Therefore, develop a kind of cheaply, possess excellent conductive performance, the conductive powder body of good weatherability just has very realistic meanings.
At present, though about respectively being the preparation and existing a lot (the Chinese patent CN200710035919.4 of research report of conductive powder body; Chinese patent CN200410021990.3; Luo Chongxiao, etc., Acta PhySico-Chimica Sinica, 2008,24 (6): 1007-1011 etc.)., these methods fundamentally solve the deficiency of existing conductive powder body performance, and ubiquity complicated process of preparation, production cost cross high deficiency, and what restricted that these conductive powder bodies further use in industry maybe.In the many reports that occurred, nickel is metal-powder because it has good physics and chemistry and electric conductivity, and price to compare other metal-powder low, become one of maximum conductive powder body of use amount now.But these research reports are often noted sight to improve on the conductivity and weatherability that nickel is conductive powder body (Chinese patent CN200710066392.1); For the production cost that how to reduce conductive powder body; The metals resources of saves valuable etc. with produce on the closely bound up link, then seldom relate to.And along with nickel is the range of application of conductive powder body and the continuous expansion of consumption, the nickel resources deposit of China relative deficiency that seems all the more.Therefore,, effectively control production cost, carry out the development that novel nickel is composite conductive powder, just become a job that has theoretical research and actual application value in order rationally to reduce the use amount of metallic nickel.
The present invention is directed to existing nickel is the deficiency that conductive powder body prepares present situation; Creatively proposed a kind of preparation method of new calcium carbonate/nickel composite conductive powder, promptly be employed in calcium carbonate nano assembling ball surface and carry out the method for in-situ reducing and prepare (shown in Figure of description 1).This method is conceived to improve the conductivity and the dispersiveness of calcium carbonate/nickel composite conductive powder; Guaranteeing that calcium carbonate/nickel composite conductive powder reaches under the prerequisite of antistatic powder to the requirement of electric conductivity; Significantly reduced the use amount of metallic nickel; Control production cost effectively, made the industrialization of calcium carbonate/nickel composite material become possibility; And, do not add any organic solvent in the reaction, when reducing production costs, also meet the Green Chemistry requirement.The present invention organically combines high activity carbonic acid calcium nanometer assembling ball and metallic nickel dexterously; Utilize the high absorption capacity of calcium carbonate nano assembling ball; Adopt the preparation method of in-situ reducing, successfully obtained the calcium carbonate/nickel composite conductive powder of controllable structure, stable performance.Simultaneously, the use of coupling agent has very positive effect to the lasting stability that improves composite conductive powder, performance such as weather-proof.The composite conductive powder that this local reduction way obtains is that existing nickel is that the metal-powder preparation method is difficult to reach at aspects such as reaction rate, product electric conductivity, dispersiveness and environment friendly.
Equipment is simple, combined coefficient is high, production cost is low because the preparation method that the present invention adopts has, the product good dispersion, conductivity is good and characteristics such as environmentally friendly, therefore, has very strong commercial viability.
Summary of the invention
The purpose of this invention is to provide a kind of calcium carbonate/nickel composite conductive powder and preparation method thereof, be used for preparing low-density conductive powder body, improve the thermal stability and the weatherability of composite material with excellent conductive performance; Adopt preparation method provided by the invention, the calcium carbonate/nickel composite conductive powder that is obtained, have raw material sources extensively, low production cost, electric conductivity be good, advantages such as good weatherability.Simultaneously, this method does not produce any hazardous waste, can save resource, reduces the pollution to environment, meets low-carbon economy and the requirement of sustainable development economy strategy.
Technical scheme of the present invention is following:
A kind of calcium carbonate/nickel composite conductive powder is characterized in that: make through following method, specifically comprise the steps:
(1) with in a certain proportion of calcium carbonate nano assembling ball and the raw material input reactor as the nickel source, be medium with water, it is even to be stirred well to system, and the ratio of the quality in calcium carbonate nano assembling ball and nickel source is 100: (0.1-1);
(2) slowly dropping is as the sodium silicate aqueous solution of coupling agent in system, and the maintenance system leaves standstill after dropwising, and the adding quality of coupling agent is the 0.05-0.5wt% of calcium carbonate nano assembling ball and nickel source gross mass;
(3) under stirring condition, in system, drip hydrazine hydrate again, regulation system temperature, the adding quality of hydrazine hydrate are calcium carbonate nano assembling ball and nickel source gross mass 1.0-5.0 times, the reaction temperature of system: 60-90 ℃;
(4) add NaOH solution adjusting pH value to system then and begin to take place in-situ reducing reaction, system generation in-situ reducing reaction pH value: pH >=13;
(5) treat the system complete reaction after, suction filtration, washing, oven dry can obtain black calcium carbonate/nickel composite conductive powder.
Described calcium carbonate/nickel composite conductive powder is characterized in that: described nickel source is selected from one or both in nickelous sulfate, the nickel chloride.
Described calcium carbonate/nickel composite conductive powder is characterized in that: the preparation method of described calcium carbonate nano assembling ball is following:
(1) get the smooth sheet glass of surfacing and be immersed in the collodion, repeat to lift, air dry, the collodion membrane template of the even 0.18-0.22mm of thickness;
(2) pellicle that step (1) is obtained is fixed in the reactor, and reactor is separated into two parts;
(3) react in following ratio: 20mL 0.10mol/L Na
2CO
3Solution and 20mL 0.10mol/L CaCl
2Solution places the both sides of barrier film assembly system respectively, reacts 20-22h under the room temperature;
(4) reaction product isolated;
(5) use the deionized water wash separated product for several times again, to product, no longer contain Ca
2+, CO
3 2-Till the plasma;
(6) product of cleaning places drier dry, obtains white powder and then is calcium carbonate nano assembling ball.
The composite material that the present invention obtains, color are black, and resistivity satisfies the requirement of antistatic powder fully, and have good dispersiveness.
The present invention has following advantage:
1, proposes first to utilize the method for in-situ reducing to prepare calcium carbonate/nickel composite conductive powder.This composite material has purity height, Stability Analysis of Structures, particle diameter is little and homogeneous, good, the no agglomeration of conductivity, be easy to advantages such as dispersion; Compare with elemental metals nickel; Guaranteeing that electric conductivity satisfies under the prerequisite of antistatic requirement; Its density has had significantly reduction especially; This reduces its consumption in actual use to expanding the range of application of composite material, and the economic value added that improves this composite conductive powder is very significant.
2, the adding of coupling agent makes that calcium carbonate nano assembling ball and nickel ion can comparatively firm combining, and has not only increased the thickness of composite conductive powder top layer metallic nickel, and makes and combine more stablely between metallic nickel and the calcium carbonate.
3, utilize local reduction way provided by the invention, the not only interpolation of no any organic reagent in the preparation process meets the Green Chemistry requirement, and reaction efficiency significantly improves, and has practiced thrift production cost greatly, possesses very strong commercial viability.
Figure of description
Fig. 1 is the synthetic sketch map of calcium carbonate/nickel composite conductive powder of the present invention.
Embodiment
Through specific embodiment the present invention is further described below.
Embodiment 1:
Get calcium carbonate nano assembling ball 10g, the sodium silicate aqueous solution that adds 0.1mL 5% is as coupling agent, again to the NiSO that wherein adds 2mol/L
46H
2O solution 50mL stirs 10min, makes nickel ion adsorbed by calcium carbonate, and it is saturated that sufficient standing makes it reach absorption; The density of hydrazine hydrate is 1.03g/mL; Quality according to adding hydrazine hydrate is that 30g takes by weighing hydrazine hydrate 29mL; In system, dropwise add, keeping system temperature is 70 ℃, uses NaOH solution to regulate and maintenance system pH=14; The nickel ion of absorption is carried out the in-situ reducing reaction, and be coated on the surface of calcium carbonate; After the system of treating is fully reacted,, can obtain black calcium carbonate/nickel composite conductive powder with products therefrom suction filtration, washing, oven dry; Product has good conductivity and dispersiveness, and resistivity is about 150 Ω/cm.
Embodiment 2
Get calcium carbonate nano assembling ball 10g, the sodium silicate aqueous solution that adds 0.5mL 5% is as coupling agent, again to the NiSO that wherein adds 2mol/L
46H
2O solution 100mL stirs 10min, makes nickel ion adsorbed by calcium carbonate, and it is saturated that sufficient standing makes it reach absorption; The density of hydrazine hydrate is 1.03g/mL; Quality according to adding hydrazine hydrate is that 12g takes by weighing hydrazine hydrate 12mL; In system, dropwise add, keeping system temperature is 70 ℃, uses NaOH solution to regulate and maintenance system pH=14; The nickel ion of absorption is carried out the in-situ reducing reaction, and be coated on the surface of calcium carbonate; After the system of treating is fully reacted,, can obtain black calcium carbonate/nickel composite conductive powder with products therefrom suction filtration, washing, oven dry; Product has good conductivity and dispersiveness, and resistivity is about 120 Ω/cm.
Embodiment 3
Get calcium carbonate nano assembling ball 10g, the sodium silicate aqueous solution that adds 1.0mL 5% is as coupling agent, again to the NiCl that wherein adds 2mol/L
26H
2O solution 40mL stirs 10min, makes nickel ion adsorbed by calcium carbonate, and it is saturated that sufficient standing makes it reach absorption; The density of hydrazine hydrate is 1.03g/mL; Quality according to adding hydrazine hydrate is that 50g takes by weighing hydrazine hydrate 49mL; In system, dropwise add, keeping system temperature is 90 ℃, uses NaOH solution to regulate and maintenance system pH=13; The nickel ion of absorption is carried out the in-situ reducing reaction, and be coated on the surface of calcium carbonate; After the system of treating is fully reacted,, can obtain black calcium carbonate/nickel composite conductive powder with products therefrom suction filtration, washing, oven dry; Product has good conductivity and dispersiveness, and resistivity is about 250 Ω/cm.
Embodiment 4
Get calcium carbonate nano assembling ball 10g, the sodium silicate aqueous solution that adds 0.1mL 5% is as coupling agent, again to the NiSO that wherein adds 2mol/L
46H
2O solution 100mL stirs 10min, makes nickel ion adsorbed by calcium carbonate, and it is saturated that sufficient standing makes it reach absorption; Quality according to adding hydrazine hydrate is that 20g takes by weighing hydrazine hydrate 19mL; In system, dropwise add, keeping system temperature is 60 ℃, uses NaOH solution to regulate and maintenance system pH=14; The nickel ion of absorption is carried out the in-situ reducing reaction, and be coated on the surface of calcium carbonate; After the system of treating is fully reacted,, can obtain black calcium carbonate/nickel composite conductive powder with products therefrom suction filtration, washing, oven dry etc.; Product has good conductivity and dispersiveness, and resistivity is about 170 Ω/cm.
Embodiment 5
Get calcium carbonate nano assembling ball 10g, the sodium silicate aqueous solution that adds 0.1mL 5% is as coupling agent, again to the NiCl that wherein adds 2mol/L
26H
2O solution 100mL stirs 10min, makes nickel ion adsorbed by calcium carbonate, and it is saturated that sufficient standing makes it reach absorption; Quality according to adding hydrazine hydrate is that 30g takes by weighing hydrazine hydrate 29mL; In system, dropwise add, keeping system temperature is 90 ℃, uses NaOH solution to regulate and maintenance system pH=13; The nickel ion of absorption is carried out the in-situ reducing reaction, and be coated on the surface of calcium carbonate; After the system of treating is fully reacted,, can obtain black calcium carbonate/nickel composite conductive powder with products therefrom suction filtration, washing, oven dry; Product has good conductivity and dispersiveness, and resistivity is about 300 Ω/cm.
Claims (3)
1. the preparation method of a calcium carbonate/nickel composite conductive powder is characterized in that: comprise the steps:
(1) with in a certain proportion of calcium carbonate nano assembling ball and the raw material input reactor as the nickel source, be medium with water, it is even to be stirred well to system, and the ratio of the quality in calcium carbonate nano assembling ball and nickel source is 100: (0.1-1);
(2) slowly dropping is as the sodium silicate aqueous solution of coupling agent in system, and the maintenance system leaves standstill after dropwising, and the adding quality of coupling agent is the 0.05-0.5wt% of calcium carbonate nano assembling ball and nickel source gross mass;
(3) under stirring condition, in system, drip hydrazine hydrate again, regulation system temperature, the adding quality of hydrazine hydrate are calcium carbonate nano assembling ball and nickel source gross mass 1.0-5.0 times, the reaction temperature of system: 60-90 ℃;
(4) add NaOH solution adjusting pH value to system then and begin to take place in-situ reducing reaction, system generation in-situ reducing reaction pH value: pH >=13;
(5) treat the system complete reaction after, suction filtration, washing, oven dry can obtain black calcium carbonate/nickel composite conductive powder.
2. the preparation method of calcium carbonate/nickel composite conductive powder according to claim 1, it is characterized in that: described nickel source is selected from one or both in nickelous sulfate, the nickel chloride.
3. the preparation method of calcium carbonate/nickel composite conductive powder according to claim 1 is characterized in that: the preparation method of described calcium carbonate nano assembling ball is following:
(1) get the smooth sheet glass of surfacing and be immersed in the collodion, repeat to lift, air dry, the collodion membrane template of the even 0.18-0.22mm of thickness;
(2) the collodion membrane template that step (1) is obtained is fixed in the reactor, and reactor is separated into two parts;
(3) react in following ratio: 20mL 0.10mol/L Na
2CO
3Solution and 20mL 0.10mol/L CaCl
2Solution places the both sides of barrier film assembly system respectively, reacts 20-22h under the room temperature;
(4) reaction product isolated;
(5) use the deionized water wash separated product for several times again, to product, no longer contain Ca
2+, CO
3 2-Till the ion;
(6) product of cleaning places drier dry, obtains white powder and then is calcium carbonate nano assembling ball.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102557609A CN101923907B (en) | 2010-08-11 | 2010-08-11 | Calcium carbonate/nickel composite conductive powder and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102557609A CN101923907B (en) | 2010-08-11 | 2010-08-11 | Calcium carbonate/nickel composite conductive powder and preparation method thereof |
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| CN101923907B true CN101923907B (en) | 2012-04-18 |
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| CN102982862B (en) * | 2012-11-30 | 2015-04-15 | 许昌学院 | Nano calcium carbonate-substrate light color conductive powder and preparation method thereof |
| CN104801723A (en) * | 2015-03-23 | 2015-07-29 | 江西九鹏科技股份有限公司 | Preparation method of calcium carbonate/copper carbonate hollow conducting materials with low density |
| CN105834446B (en) * | 2016-04-12 | 2017-12-26 | 同济大学 | A kind of synthetic method of ultra-thin stratiform NiO CoOx nanometer sheets load NiCo nano compositions |
| CN111331149B (en) * | 2020-03-09 | 2022-08-05 | 陕西师范大学 | Method for preparing hollow Pt nanospheres by taking spherical calcium carbonate as template |
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| JP2003146697A (en) * | 2001-11-13 | 2003-05-21 | Sanwa Denzai:Kk | Dielectric composition |
| US7041239B2 (en) * | 2003-04-03 | 2006-05-09 | Valence Technology, Inc. | Electrodes comprising mixed active particles |
| CN101259401B (en) * | 2004-11-11 | 2010-06-23 | 中国科学院化学研究所 | Method for preparing hollow ball and hollow ball with complex structure by template method |
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Effective date of registration: 20210705 Address after: 247000 taopo village, Meijie Town, Guichi District, Chizhou City, Anhui Province Patentee after: Chizhou Guixing non mineral New Material Co.,Ltd. Address before: 247100 No.1 Education Park, Chizhou City, Anhui Province Patentee before: CHIZHOU University |
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Denomination of invention: A calcium carbonate/nickel composite conductive powder and its preparation method Effective date of registration: 20230918 Granted publication date: 20120418 Pledgee: Agricultural Bank of China Limited by Share Ltd. Chizhou branch Pledgor: Chizhou Guixing non mineral New Material Co.,Ltd. Registration number: Y2023980057160 |
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| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20120418 Pledgee: Agricultural Bank of China Limited by Share Ltd. Chizhou branch Pledgor: Chizhou Guixing non mineral New Material Co.,Ltd. Registration number: Y2023980057160 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A calcium carbonate/nickel composite conductive powder and its preparation method Granted publication date: 20120418 Pledgee: Agricultural Bank of China Limited by Share Ltd. Chizhou branch Pledgor: Chizhou Guixing non mineral New Material Co.,Ltd. Registration number: Y2024980040270 |