CN107248454A - A kind of graphene crystalline material and preparation method and application - Google Patents

A kind of graphene crystalline material and preparation method and application Download PDF

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Publication number
CN107248454A
CN107248454A CN201710420243.4A CN201710420243A CN107248454A CN 107248454 A CN107248454 A CN 107248454A CN 201710420243 A CN201710420243 A CN 201710420243A CN 107248454 A CN107248454 A CN 107248454A
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graphene
crystalline material
parts
ferroso
iron powder
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唐春霞
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Sun Cuifang
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唐春霞
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Priority to CN201710420243.4A priority Critical patent/CN107248454A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of graphene crystalline material, it is made up of the component of following parts by weight:20 parts of graphene, 0.1 part~1.2 parts of ferroso-ferric oxide, 0.1 part~1.2 parts of iron powder, 0.1 part~0.5 part of activated carbon.Capacitor manufactured by graphene crystalline material of the present invention shows good electrochemical behavior, and specific capacity can reach 954F/g all in 300F/g, with very excellent energy-storage property;Moreover, the preparation technology of graphene crystalline material of the present invention is easy, safe and environment-friendly, raw material are cheap, be easy to get, and cost is low, are adapted to industrialization production.

Description

A kind of graphene crystalline material and preparation method and application
Technical field
The present invention relates to a kind of graphene crystalline material and preparation method and application.
Background technology
Capacitor, is a kind of new type of energy storage device, in the side such as portable electric appts, hybrid vehicle, Electric power car Face is in an increasingly wide range of applications.
However, due to being limited by electrode material performance, the energy-storage property of current capacitor is still relatively low, specific capacity is led to 200F/g~400F/g often is can only achieve, such as:103680974 A etc. of A, CN of Chinese patent CN 105489398.
In order to further improve the energy-storage property of capacitor, higher specific capacity is reached, a kind of new electrode of exploitation is needed badly Material.
The content of the invention
It is an object of the invention to provide a kind of graphene crystalline material, its can produce specific capacity be up to 304F/g~ 954F/g capacitor, energy-storage property is very excellent.
A kind of graphene crystalline material that the present invention is provided, it is made up of the component of following parts by weight:Graphene 20 Part, 0.1 part~1.2 parts of ferroso-ferric oxide, 0.1 part~1.2 parts of iron powder, 0.1 part~0.5 part of activated carbon.
Further, it is made up of the component of following parts by weight:20 parts of graphene, ferroso-ferric oxide 1.0 parts~1.2 Part, 0.1 part~0.2 part of iron powder, 0.1 part~0.2 part of activated carbon.
Further, it is made up of the component of following parts by weight:It is made up of the component of following parts by weight:Stone Black 20 parts of alkene, 1.0 parts of ferroso-ferric oxide, 0.2 part of iron powder, 0.2 part of activated carbon.
Further, described graphene is selected from single-layer graphene, bilayer graphene, few layer graphene, multi-layer graphene In any one or it is two or more.
Further, the particle diameter of the ferroso-ferric oxide is 80nm~500nm, the particle diameter of the iron powder for 80nm~ 500nm;It is preferred that, the particle diameter of the ferroso-ferric oxide is 150nm~200nm, and the particle diameter of the iron powder is 80nm~120nm.
Further, the particle diameter of the activated carbon is 10nm~50nm.
Further, described graphene crystalline material is made of using following methods:Graphene is taken, is dispersed in water, 90 ± 5 DEG C are heated to, ultrasonically treated 30 minutes, is then maintained at a temperature of 90 ± 5 DEG C, ferroso-ferric oxide, iron powder is added, mixed After even, activated carbon is added, is stirred 5 hours, 30 minutes are stood, filtered, drying produces graphene crystalline material.
Further to the ultrasonically treated power is 500W, and the speed of the stirring is 500 revs/min.
Present invention also offers application of the above-mentioned graphene crystalline material in manufacture capacitor.
A kind of capacitor that the present invention is provided, it is made of using following methods:
A, by graphene crystalline material, polytetrafluoroethylene (PTFE), the conductive black described in claim 1~8 any one, according to Weight proportion 90:5:5 or 85:5:10 are well mixed, plus appropriate solvent, are coated on copper foil, after drying, rolling film, cutting, system Into electrode slice;
B, by electrode slice, barrier film, electrode slice, lamination assembling is into battery core in sequence, then with battery housing seal battery core, with Liquid injection port is sealed, electricity is obtained toward the sulfuric acid that 2mol/L is injected in battery container by the liquid injection port that is arranged on battery container afterwards Container.
Capacitor manufactured by graphene crystalline material of the present invention shows good electrochemical behavior, and specific capacity all exists More than 300F/g, can reach 954F/g, with very excellent energy-storage property;Moreover, graphene crystalline material of the present invention Preparation technology it is easy, safe and environment-friendly, raw material are cheap, be easy to get, and cost is low, are adapted to industrialization production.
Obviously, according to the above of the present invention, according to the ordinary technical knowledge and customary means of this area, do not departing from Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification of other diversified forms can also be made, replaces or changes.
Below by way of embodiment, the above to the present invention is described in further detail again;But should not be by This scope for being interpreted as above-mentioned theme of the invention is only limitted to following example;The technology that all designs based on the present invention are realized is equal Belong to the scope of the present invention.
Embodiment
The raw material that is used in the specific embodiment of the invention, equipment are known product, are obtained by buying commercially available prod.
Embodiment 1
1st, the preparation of graphene crystalline material
Bilayer graphene 20g is taken, is dispersed in 100ml water, 90 ± 5 DEG C, ultrasonically treated (power 500W) 30 are heated to Minute, then it is maintained at a temperature of 90 ± 5 DEG C, adds ferroso-ferric oxide (particle diameter:150nm~200nm) 1g, iron powder (particle diameter: 80nm~120nm) 0.2g, after mixing, add activated carbon (particle diameter:10nm~50nm) 0.2g, is stirred 5 hours, stir speed (S.S.) 500 revs/min, 30 minutes are stood, is filtered, drying produces graphene crystalline material M1.
2nd, graphene crystalline material is used to manufacture capacitor
A, by above-mentioned graphene crystalline material M1, polytetrafluoroethylene (PTFE), conductive black, according to weight proportion 90:5:5 mixing are equal It is even, plus appropriate solvent, it is coated on copper foil, after drying, rolling film, cutting, electrode slice is made;
B, by electrode slice, barrier film, electrode slice, lamination assembling is into battery core in sequence, then with battery housing seal battery core, with Liquid injection port is sealed, electricity is obtained toward the sulfuric acid that 2mol/L is injected in battery container by the liquid injection port that is arranged on battery container afterwards Container C1.
Embodiment 2
1st, the preparation of graphene crystalline material
Bilayer graphene 20g is taken, is dispersed in 100ml water, 90 ± 5 DEG C, ultrasonically treated (power 500W) 30 are heated to Minute, then it is maintained at a temperature of 90 ± 5 DEG C, adds ferroso-ferric oxide (particle diameter:400nm~500nm) 1g, iron powder (particle diameter: 400nm~500nm) 0.2g, after mixing, add activated carbon (particle diameter:10nm~50nm) 0.2g, is stirred 5 hours, stir speed (S.S.) 500 revs/min, 30 minutes are stood, is filtered, drying produces graphene crystalline material M2.
2nd, graphene crystalline material is used to manufacture capacitor
A, by above-mentioned graphene crystalline material M2, polytetrafluoroethylene (PTFE), conductive black, according to weight proportion 80:10:10 mixing Uniformly, plus appropriate solvent, it is coated on copper foil, after drying, rolling film, cutting, electrode slice is made;
B, by electrode slice, barrier film, electrode slice, lamination assembling is into battery core in sequence, then with battery housing seal battery core, with Liquid injection port is sealed, electricity is obtained toward the sulfuric acid that 2mol/L is injected in battery container by the liquid injection port that is arranged on battery container afterwards Container C2.
Embodiment 3
1st, the preparation of graphene crystalline material
Bilayer graphene 20g is taken, is dispersed in 100ml water, 90 ± 5 DEG C, ultrasonically treated (power 500W) 30 are heated to Minute, then it is maintained at a temperature of 90 ± 5 DEG C, adds ferroso-ferric oxide (particle diameter:80nm~120nm) 1g, iron powder (particle diameter: 80nm~120nm) 0.2g, after mixing, add activated carbon (particle diameter:10nm~50nm) 0.2g, is stirred 5 hours, stir speed (S.S.) 500 revs/min, 30 minutes are stood, is filtered, drying produces graphene crystalline material M3.
2nd, graphene crystalline material is used to manufacture capacitor
A, by above-mentioned graphene crystalline material M3, polytetrafluoroethylene (PTFE), conductive black, according to weight proportion 85:10:5 mixing Uniformly, plus appropriate solvent, it is coated on copper foil, after drying, rolling film, cutting, electrode slice is made;
B, by electrode slice, barrier film, electrode slice, lamination assembling is into battery core in sequence, then with battery housing seal battery core, with Liquid injection port is sealed, electricity is obtained toward the sulfuric acid that 2mol/L is injected in battery container by the liquid injection port that is arranged on battery container afterwards Container C3.
Embodiment 4
1st, the preparation of graphene crystalline material
Bilayer graphene 20g is taken, is dispersed in 100ml water, 90 ± 5 DEG C, ultrasonically treated (power 500W) 30 are heated to Minute, then it is maintained at a temperature of 90 ± 5 DEG C, adds ferroso-ferric oxide (particle diameter:150nm~200nm) 1g, iron powder (particle diameter: 80nm~120nm) 0.2g, after mixing, add activated carbon (particle diameter:10nm~50nm) 0.2g, is stirred 5 hours, stir speed (S.S.) 500 revs/min, 30 minutes are stood, is filtered, drying produces graphene crystalline material M4.
2nd, graphene crystalline material is used to manufacture capacitor
A, by above-mentioned graphene crystalline material M4, polytetrafluoroethylene (PTFE), conductive black, according to weight proportion 85:5:10 mixing Uniformly, plus appropriate solvent, it is coated on copper foil, after drying, rolling film, cutting, electrode slice is made;
B, by electrode slice, barrier film, electrode slice, lamination assembling is into battery core in sequence, then with battery housing seal battery core, with Liquid injection port is sealed, electricity is obtained toward the sulfuric acid that 2mol/L is injected in battery container by the liquid injection port that is arranged on battery container afterwards Container C4.
Embodiment 5
1st, the preparation of graphene crystalline material
Bilayer graphene 20g is taken, is dispersed in 100ml water, 90 ± 5 DEG C, ultrasonically treated (power 500W) 30 are heated to Minute, then it is maintained at a temperature of 90 ± 5 DEG C, adds ferroso-ferric oxide (particle diameter:150nm~200nm) 0.2g, iron powder (grain Footpath:80nm~120nm) 1g, after mixing, add activated carbon (particle diameter:200nm~300nm) 0.2g, is stirred 5 hours, stirring speed 500 revs/min of rate, stands 30 minutes, filters, and drying produces graphene crystalline material M5.
2nd, graphene crystalline material is used to manufacture capacitor
A, by above-mentioned graphene crystalline material M5, polytetrafluoroethylene (PTFE), conductive black, according to weight proportion 90:5:5 mixing are equal It is even, plus appropriate solvent, it is coated on copper foil, after drying, rolling film, cutting, electrode slice is made;
B, by electrode slice, barrier film, electrode slice, lamination assembling is into battery core in sequence, then with battery housing seal battery core, with Liquid injection port is sealed, electricity is obtained toward the sulfuric acid that 2mol/L is injected in battery container by the liquid injection port that is arranged on battery container afterwards Container C5.
Embodiment 6
1st, the preparation of graphene crystalline material
Bilayer graphene 20g is taken, is dispersed in 100ml water, 90 ± 5 DEG C, ultrasonically treated (power 500W) 30 are heated to Minute, then it is maintained at a temperature of 90 ± 5 DEG C, adds activated carbon (particle diameter:200nm~300nm) 0.2g, after mixing, then add Enter ferroso-ferric oxide (particle diameter:150nm~200nm) 0.6g, iron powder (particle diameter:150nm~200nm) 0.6g, stirs 5 hours, stirs 200 revs/min of speed is mixed, 30 minutes are stood, filtered, drying produces graphene crystalline material M6.
2nd, graphene crystalline material is used to manufacture capacitor
A, by above-mentioned graphene crystalline material M6, polytetrafluoroethylene (PTFE), conductive black, according to weight proportion 85:5:10 mixing Uniformly, plus appropriate solvent, it is coated on copper foil, after drying, rolling film, cutting, electrode slice is made;
B, by electrode slice, barrier film, electrode slice, lamination assembling is into battery core in sequence, then with battery housing seal battery core, with Liquid injection port is sealed, electricity is obtained toward the sulfuric acid that 2mol/L is injected in battery container by the liquid injection port that is arranged on battery container afterwards Container C6.
By tests below example, to illustrate beneficial effects of the present invention.
Test example
To capacitor C1~C6 manufactured by embodiment 1~6, respectively 0.1,0.2,0.5,1.0,2.0A/g electric current it is close Degree is lower to carry out charge-discharge test, obtains the test result of specific capacity, is shown in Table 1.
The test result of table 1, specific capacity
The above results show, in cyclic process, and the capacitor manufactured by graphene crystalline material of the present invention shows good Good electrochemical behavior, specific capacity can reach 954F/g all in more than 300F/g, with very excellent energy-storage property.
In summary, the capacitor manufactured by graphene crystalline material of the present invention shows good electrochemical behavior, than Capacity can reach 954F/g all in more than 300F/g, with very excellent energy-storage property;Moreover, graphene of the present invention The preparation technology of crystalline material is easy, safe and environment-friendly, and raw material are cheap, be easy to get, and cost is low, are adapted to industrialization production.

Claims (10)

1. a kind of graphene crystalline material, it is characterised in that:It is made up of the component of following parts by weight:20 parts of graphene, 0.1 part~1.2 parts of ferroso-ferric oxide, 0.1 part~1.2 parts of iron powder, 0.1 part~0.5 part of activated carbon.
2. graphene crystalline material according to claim 1, it is characterised in that:It is the component group by following parts by weight Into:20 parts of graphene, 1.0 parts~1.2 parts of ferroso-ferric oxide, 0.1 part~0.2 part of iron powder, 0.1 part~0.2 part of activated carbon.
3. graphene crystalline material according to claim 2, it is characterised in that:It is the component group by following parts by weight Into:It is made up of the component of following parts by weight:20 parts of graphene, 1.0 parts of ferroso-ferric oxide, 0.2 part of iron powder, activated carbon 0.2 part.
4. the graphene crystalline material according to claims 1 to 3 any one, it is characterised in that:Described graphene choosing From any one in single-layer graphene, bilayer graphene, few layer graphene, multi-layer graphene or two or more.
5. the graphene crystalline material according to claims 1 to 3 any one, it is characterised in that:The ferroso-ferric oxide Particle diameter be 80nm~500nm, the particle diameter of the iron powder is 80nm~500nm;It is preferred that, the particle diameter of the ferroso-ferric oxide is 150nm~200nm, the particle diameter of the iron powder is 80nm~120nm.
6. the graphene crystalline material according to claims 1 to 3 any one, it is characterised in that:The grain of the activated carbon Footpath is 10nm~50nm.
7. the graphene crystalline material according to claims 1 to 3 any one, it is characterised in that:Described graphene is brilliant Body material is made of using following methods:Graphene is taken, is dispersed in water, 90 ± 5 DEG C are heated to, ultrasonically treated 30 minutes, so After be maintained at a temperature of 90 ± 5 DEG C, add ferroso-ferric oxide, iron powder, after mixing, add activated carbon, stir 5 hours, it is quiet Put 30 minutes, filter, drying produces graphene crystalline material.
8. graphene crystalline material according to claim 7, it is characterised in that:The ultrasonically treated power is 500W, The speed of the stirring is 500 revs/min.
9. application of the graphene crystalline material in manufacture capacitor described in claim 1~8 any one.
10. a kind of capacitor, it is characterised in that:It is made of using following methods:
A, by graphene crystalline material, polytetrafluoroethylene (PTFE), the conductive black described in claim 1~8 any one, according to weight Proportioning 90:5:5 or 85:5:10 are well mixed, plus appropriate solvent, are coated on copper foil, and after drying, rolling film, cutting, electricity is made Pole piece;
B, by electrode slice, barrier film, electrode slice, lamination assembling is into battery core in sequence, then logical then with battery housing seal battery core The liquid injection port being arranged on battery container is crossed toward the sulfuric acid of injection 2mol/L in battery container, liquid injection port is sealed, obtains capacitor.
CN201710420243.4A 2017-06-06 2017-06-06 A kind of graphene crystalline material and preparation method and application Pending CN107248454A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102568641A (en) * 2010-12-29 2012-07-11 海洋王照明科技股份有限公司 Preparation method for graphene composite material loaded with nano metal particles
CN102623692A (en) * 2012-03-21 2012-08-01 新疆大学 Method for preparing anode material of ferroferric oxide and carbon composite lithium battery
CN103833032A (en) * 2014-03-11 2014-06-04 中国第一汽车股份有限公司 Graphene-based composite cathode material
US20140340818A1 (en) * 2011-11-10 2014-11-20 The Regent Of The University Of Colorado A Body Corporate Supercapacitor Devices Having Composite Electrodes Formed By Depositing Metal Oxide Pseudocapacitor Materials Onto Carbon Substrates
CN105702957A (en) * 2014-11-27 2016-06-22 中国科学院大连化学物理研究所 Method for changing potential of carbon-based material electrode
CN105762362A (en) * 2016-05-23 2016-07-13 四川大学 Carbon-coated ferroferric oxide/nitrogen-doped grapheme composite material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102568641A (en) * 2010-12-29 2012-07-11 海洋王照明科技股份有限公司 Preparation method for graphene composite material loaded with nano metal particles
US20140340818A1 (en) * 2011-11-10 2014-11-20 The Regent Of The University Of Colorado A Body Corporate Supercapacitor Devices Having Composite Electrodes Formed By Depositing Metal Oxide Pseudocapacitor Materials Onto Carbon Substrates
CN102623692A (en) * 2012-03-21 2012-08-01 新疆大学 Method for preparing anode material of ferroferric oxide and carbon composite lithium battery
CN103833032A (en) * 2014-03-11 2014-06-04 中国第一汽车股份有限公司 Graphene-based composite cathode material
CN105702957A (en) * 2014-11-27 2016-06-22 中国科学院大连化学物理研究所 Method for changing potential of carbon-based material electrode
CN105762362A (en) * 2016-05-23 2016-07-13 四川大学 Carbon-coated ferroferric oxide/nitrogen-doped grapheme composite material and preparation method thereof

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