CN108155025A - A kind of high-density graphite alkene material, preparation method and its stored energy application - Google Patents
A kind of high-density graphite alkene material, preparation method and its stored energy application Download PDFInfo
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- CN108155025A CN108155025A CN201711433461.8A CN201711433461A CN108155025A CN 108155025 A CN108155025 A CN 108155025A CN 201711433461 A CN201711433461 A CN 201711433461A CN 108155025 A CN108155025 A CN 108155025A
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- graphite alkene
- density graphite
- density
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- alkene material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
A kind of high-density graphite alkene material, preparation method and its stored energy application, are related to ultracapacitor and lithium ion battery electrode material field.The graphene prepared using Physical or chemical method is raw material, pass through the mechanical processes such as crushing or ball milling, highdensity grapheme material is obtained, good chemical property is shown when this high-density graphite alkene material is as lithium ion battery and electrode material for super capacitor.It finds after tested, as lithium ion battery electrode material in use, specific discharge capacity is up to 800 1100mAh g‑1, volume and capacity ratio is up to 1000 1500mAh cm‑3；As electrode material for super capacitor in use, specific discharge capacity is up to 130 180F g‑1, volume and capacity ratio is up to 220 320F cm‑3；There is excellent high rate performance and cyclical stability simultaneously.
Description
Technical field
The present invention relates to ultracapacitor and lithium ion battery electrode material field, more particularly to a kind of high-density graphite alkene
Material, preparation method and its stored energy application.
Background technology
Ultracapacitor and lithium ion battery are the electrochemical energy storage devices being widely used at present, have service life it is long,
The advantages such as energy or power density height, thus have in fields such as electric system, communication, new energy, electric vehicles and widely should
Use prospect.Electrode material is the core component of ultracapacitor and lithium ion battery, thus develop high performance electrode material into
For the task of top priority.
Graphene theoretical specific surface area is big, and theoretical capacity is high, and electric conductivity is excellent, stable chemical performance, therefore becomes
One of research hotspot of electrode material of ultracapacitor and lithium ion battery [Wang Qian, Yan Jun, Fan
Zhuangjun.Carbon materials for high volumetric performance supercapacitors:
Design, progress, challenges and opportunities [J] .Energy Environment Science,
2016,9：729—762].But the bulk density of graphene is low, and when leading to it as electrode material, the volume and capacity ratio of device
It is very low, it is unfavorable for realizing miniaturization and the portability of device.
In recent years, electrode material density is improved, and then improves device volume and holds quantifier elimination as hot spot.Yang Quanhong, model
Strong army, Ruoff etc. have prepared high-density graphite alkene assembly by the methods of vacuum drying, template, vacuum filtration, made
Standby grapheme material density is 1-1.5g cm-3, volume and capacity ratio is 170-400F cm-3.But the high density reported at present
The problems such as preparation method generally existing technological process of grapheme material is complicated, and aftertreatment technology takes, is unfavorable for industrialized
It realizes.
Invention content
For the above problem of the prior art, the present invention solves the preparation process mistake of existing high-density graphite alkene material
In the complicated and time consumption the problem of, it is made as follows：
Step 1：With thickness in 0.4-5nm, length dimension is starting material in 5-20 μm of graphene；
Step 2：Graphene obtained by step 1 is put into pulverizer or ball grinder, under certain atmosphere, is cut
Crushing or ball milling for a period of time, obtain high-density graphite alkene material.
Further preferred embodiment is the present invention：The one kind of the atmosphere in air, nitrogen, argon gas or vacuum.
Further preferred embodiment is the present invention：The Ball-milling Time is 0.5-40 hours, and abrading-ball is agate.
The gained high-density graphite alkene material of the present invention is by relative to that material stock thickness is thicker, length dimension is shorter
Burl block forms the block of different-grain diameter；Multiple blocks form flower-like structure.
In addition the present invention also provides method prepare high-density graphite alkene as ultracapacitor and lithium ion battery battery
The application of pole material.
The present invention prepares highdensity Graphene electrodes material using the densification effects of mechanicals efforts.Pass through simple machine
Tool processing, can effectively improve the apparent density and bulk density of material, and prepared material is without last handling process, greatly
Shorten preparation time greatly.The mechanicals efforts such as crushing or the shearing in mechanical milling process, fault can make the lamella knot of graphene
Structure is hit tight, and while effectively improving material bulk density, a large amount of defect sturcture and portion can also be introduced on graphene sheet layer
Divide oxygen-containing functional group (can obtain part oxygen-containing functional group under air conditions).The graphene of this high defect has very high work
Property can effectively improve the specific discharge capacity of material, while graphene when being used as ultracapacitor or lithium ion battery electrode material
The high density of material also substantially increases its volume and capacity ratio.It finds after tested, prepared high-density graphite alkene material conduct
Lithium ion battery electrode material in use, specific discharge capacity up to 800-1100mAh g-1, volume and capacity ratio is up to 1000-
1500mAh cm-3；As electrode material for super capacitor in use, specific discharge capacity is up to 130-180F g-1, volume specific volume
Amount is up to 220-320F cm-3, while also there is superior high rate performance and cyclical stability.
Description of the drawings
The scanning electron microscope (SEM) photograph of graphene of the attached drawing 1 for thermal expansion graphene and by 8 hours air ball-milling treatments.
Attached drawing 2 is the infrared analysis comparison diagram before and after graphene ball-milling treatment.
Attached drawing 3 is high rate performance figure of Fig. 1 graphenes as electrode material for super capacitor.
Graphene of the attached drawing 4 for thermal expansion graphene and by 21 hours argon gas ball-milling treatments is as lithium ion cell electrode
The cycle performance figure of material.
The transmission electron microscope picture of graphene that attached drawing 5 is prepared for ultrasound stripping.(b) it is the amplification in (a).
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and examples, but the present invention is not limited to following embodiments.
Embodiment 1
Graphite oxide is prepared by Hummers methods, graphene is prepared using rapid thermal expansion, is put into agate jar
(agate ball has two kinds of sizes of size to ball milling, and diameter is respectively the matter of 10mm and 6mm, big ball and bead within 8 hours in air atmosphere
Amount is than being 2：1) high-density graphite alkene material, is obtained.
As shown in 1 scanning electron microscope of attached drawing, ball-milling treatment is after 8 hours, and significant change occurs for graphene pattern, and size is by 12 μm
3 μm are reduced to, thickness also greatly increases, and caking phenomenon occurs.
As shown in 2 infrared test figure of attached drawing, ball milling is after 8 hours under air atmosphere, the oxygen-containing function such as carboxyl, carbonyl, epoxy
The content of group significantly increases.
As 3 ultracapacitor high rate performance test result of attached drawing shows in 1Ag-1Under current density, graphene before ball milling
Specific discharge capacity and volume and capacity ratio are respectively 165F g-1With 95F cm-3, the quality specific volume of graphene after air ball milling 8 hours
Amount and volume and capacity ratio are respectively 183F g-1With 320F cm-3.And material has excellent high rate performance.
Embodiment 2
Graphite oxide is prepared by Hummers methods, graphene is prepared using reducing agent reduction, is put into ball grinder in argon
Ball milling 21 hours under gas atmosphere obtain high-density graphite alkene material.
As 4 cycle performance of lithium ion battery test result of attached drawing shows in 50mA g-1Under current density, graphite before ball milling
The specific discharge capacity and volume and capacity ratio of alkene are respectively 1010mAh g-1With 581mAh cm-3；Graphite after argon gas ball milling 21 hours
The specific discharge capacity and volume and capacity ratio of alkene are respectively 990mAh g-1With 1450mAh cm-3。
Embodiment 3
Graphene is prepared by ultrasonic stripping method, is put into pulverizer and crushes in a nitrogen atmosphere 5 hours, obtain high density
Grapheme material.
As shown in 5 transmission electron microscope of attached drawing, after being ultrasonically treated 1 hour, the graphene removed, size is 4 μm.
During as electrode material for super capacitor, in 1Ag-1Under current density, nitrogen crushes the graphene mass ratio of 5 hours
Capacity and volume and capacity ratio are respectively 150F g-1With 240F cm-3；In 10A g-1Under current density, electric discharge specific discharge capacity and
Volume and capacity ratio is respectively 130F g-1With 210F cm-3。
Embodiment 4
Graphene is prepared by ultrasonic lift-off processing, is put into ball mill and is crushed 10 hours under vacuum atmosphere, obtain height
Density graphite alkene material.
During as lithium ion battery electrode material, in 20mAg-1Under current density, the vacuum ball milling graphene matter of 10 hours
It is respectively 1100mAh g to measure specific capacity and volume and capacity ratio-1With 1650mAh cm-3；In 100mAg-1Under current density, matter of discharging
It is respectively 900mAh g to measure specific capacity and volume and capacity ratio-1With 1350mAh cm-3。
Embodiment 5
Graphene is prepared by ultrasonic lift-off processing, is put into pulverizer and crushes in air atmosphere 36 hours, obtain height
Density graphite alkene material.
During as electrode material for super capacitor, in 1Ag-1Under current density, air crushes the graphene quality of 36 hours
Specific capacity and volume and capacity ratio are respectively 120F g-1With 185F cm-3；In 10Ag-1Under current density, electric discharge specific discharge capacity and
Volume and capacity ratio is respectively 100F g-1With 150F cm-3。
Presently preferred embodiments of the present invention is illustrated above, but the present invention is not limited to the embodiment,
Those skilled in the art can also make various equivalent modifications or replacement under the premise of without prejudice to spirit of the invention,
These equivalent modifications or replacement are all contained in the application claim limited range.
Claims (6)
1. a kind of preparation method of high-density graphite alkene material, which is characterized in that include the following steps：
Step 1：With thickness in 0.4-5nm, length dimension is starting material in 5-20 μm of graphene；
Step 2：Graphene obtained by step 1 is put into pulverizer or ball grinder, under certain atmosphere, carries out cutting and grinding
Or ball milling is for a period of time, obtains high-density graphite alkene material.
A kind of 2. preparation method of high-density graphite alkene material described in accordance with the claim 1, which is characterized in that the atmosphere
One kind in air, nitrogen, argon gas or vacuum.
3. the preparation method of a kind of high-density graphite alkene material described in accordance with the claim 1, which is characterized in that during the ball milling
Between for 0.5-40 hours, abrading-ball is agate.
A kind of 4. preparation method of high-density graphite alkene material described in accordance with the claim 1, which is characterized in that gained high density
Grapheme material is the block by forming different-grain diameter relative to the particle from caking that material stock thickness is thicker, length dimension is shorter；
Multiple blocks form flower-like structure.
5. according to the application of high-density graphite alkene material that any one of claim 1-4 placements are prepared, as super capacitor
The application of device and lithium ion battery electrode material.
6. the high-density graphite alkene material being prepared according to any one of claim 1-4 placements.
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| CN201711433461.8A CN108155025B (en) | 2017-12-26 | 2017-12-26 | High-density graphene material, preparation method and energy storage application thereof |
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| CN108155025B CN108155025B (en) | 2020-09-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109179384A (en) * | 2018-09-11 | 2019-01-11 | 太原理工大学 | A kind of high-density graphite alkene and preparation method thereof |
| CN112086632A (en) * | 2020-09-18 | 2020-12-15 | 杭州高烯科技有限公司 | Defect-state disordered-layer stacked graphene assembled battery material and preparation method thereof |
| CN112079356A (en) * | 2020-09-04 | 2020-12-15 | 北京化工大学 | Modified activated carbon material, preparation method and application of modified activated carbon material in super capacitor |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870466A (en) * | 2010-05-20 | 2010-10-27 | 北京化工大学 | Preparation method of electrode material graphene nanometer sheet and electrode sheet prepared therefrom |
| CN101937994A (en) * | 2010-08-25 | 2011-01-05 | 天津大学 | Graphene/aluminum composite cathode material of lithium ion battery and preparation method thereof |
| CN102515152A (en) * | 2011-12-23 | 2012-06-27 | 深圳市贝特瑞纳米科技有限公司 | Method for preparing spheroidal graphene |
| CN103011143A (en) * | 2012-12-20 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | Graphene and fabrication method thereof and super capacitor |
| CN103456959A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Graphene composite material and preparation method thereof |
| CN103682279A (en) * | 2013-12-27 | 2014-03-26 | 浙江大学 | Silicon-based composite lithium ion battery negative electrode material as well as preparation method and application of silicon-based composite lithium ion battery negative electrode material |
| KR20140070172A (en) * | 2012-11-30 | 2014-06-10 | 한국전기연구원 | Method for carbon particles shape-control for high-power energy storage device and energy storage device made by the method |
| CN104073674A (en) * | 2014-06-20 | 2014-10-01 | 哈尔滨翔科新材料有限公司 | Preparation method of graphene aluminum-based composite material |
| CN106824404A (en) * | 2016-12-20 | 2017-06-13 | 西北稀有金属材料研究院 | The method of raising ito powder apparent density and the tap density of being sieved by dry ball milling |
-
2017
- 2017-12-26 CN CN201711433461.8A patent/CN108155025B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870466A (en) * | 2010-05-20 | 2010-10-27 | 北京化工大学 | Preparation method of electrode material graphene nanometer sheet and electrode sheet prepared therefrom |
| CN101937994A (en) * | 2010-08-25 | 2011-01-05 | 天津大学 | Graphene/aluminum composite cathode material of lithium ion battery and preparation method thereof |
| CN102515152A (en) * | 2011-12-23 | 2012-06-27 | 深圳市贝特瑞纳米科技有限公司 | Method for preparing spheroidal graphene |
| CN103456959A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Graphene composite material and preparation method thereof |
| KR20140070172A (en) * | 2012-11-30 | 2014-06-10 | 한국전기연구원 | Method for carbon particles shape-control for high-power energy storage device and energy storage device made by the method |
| CN103011143A (en) * | 2012-12-20 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | Graphene and fabrication method thereof and super capacitor |
| CN103682279A (en) * | 2013-12-27 | 2014-03-26 | 浙江大学 | Silicon-based composite lithium ion battery negative electrode material as well as preparation method and application of silicon-based composite lithium ion battery negative electrode material |
| CN104073674A (en) * | 2014-06-20 | 2014-10-01 | 哈尔滨翔科新材料有限公司 | Preparation method of graphene aluminum-based composite material |
| CN106824404A (en) * | 2016-12-20 | 2017-06-13 | 西北稀有金属材料研究院 | The method of raising ito powder apparent density and the tap density of being sieved by dry ball milling |
Non-Patent Citations (1)
| Title |
|---|
| 石富: "《稀土永磁材料制备技术》", 31 January 2007 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109179384A (en) * | 2018-09-11 | 2019-01-11 | 太原理工大学 | A kind of high-density graphite alkene and preparation method thereof |
| CN112079356A (en) * | 2020-09-04 | 2020-12-15 | 北京化工大学 | Modified activated carbon material, preparation method and application of modified activated carbon material in super capacitor |
| CN112086632A (en) * | 2020-09-18 | 2020-12-15 | 杭州高烯科技有限公司 | Defect-state disordered-layer stacked graphene assembled battery material and preparation method thereof |
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| CN108155025B (en) | 2020-09-04 |
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