CN106098408A - A kind of preparation method of lithium ion super capacitor grapheme composite positive electrode material - Google Patents

A kind of preparation method of lithium ion super capacitor grapheme composite positive electrode material Download PDF

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CN106098408A
CN106098408A CN201610616219.3A CN201610616219A CN106098408A CN 106098408 A CN106098408 A CN 106098408A CN 201610616219 A CN201610616219 A CN 201610616219A CN 106098408 A CN106098408 A CN 106098408A
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lithium ion
super capacitor
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graphene
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肖丽芳
钟玲珑
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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
    • H01G11/50Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • 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
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/46Metal oxides
    • 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)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides the preparation method of a kind of lithium ion super capacitor grapheme composite positive electrode material.Rapid including the following steps: step (1) is by Li2CO3And MoO3Mixing, puts into Muffle reaction in furnace after mix homogeneously, reaction obtains Li after terminating2MoO4Material;Step (2) by graphite oxide with obtain Li2MoO4Material mixing, puts into the Muffle reaction in furnace of hydrogen nitrogen mixed gas atmosphere protection after uniform mix homogeneously, reaction obtains Graphene after terminating and is combined Li2MoO3Material.There is advantages that (1) Graphene is combined Li2MoO3Material makes negative pole need not add the pre-embedding lithium technique of lithium sheet or complexity as the positive pole of lithium ion super capacitor, simplifies preparation technology, reduces cost;(2) Graphene is combined Li2MoO3Material has high connductivity, high-specific surface area can effectively substitute conventional activated carbon positive electrode, it is achieved high-energy-density and high power density.

Description

A kind of preparation method of lithium ion super capacitor grapheme composite positive electrode material
Technical field
The invention belongs to lithium ion super capacitor technical field, relate to a kind of lithium ion super capacitor positive electrode Preparation method.
Background technology
In recent years, lithium rechargeable battery has obtained the biggest development, and this battery cathode generally uses the charcoal elements such as graphite Material, positive pole uses cobalt acid lithium, LiMn2O4 etc. containing lithium metal oxide.After this set of cells is filled with, during charging, negative pole is to positive pole Lithium ion is provided, and the lithium ion of positive pole returns negative pole when electric discharge, is therefore referred to as " rocking chair type battery ".With use metal The lithium battery of lithium is compared, and this battery has high security and the feature of high cycle life.
But, owing to positive electrode is susceptible to the deformation of structure, therefore, lithium ion secondary electricity during removal lithium embedded The cycle life in pond is still restricted.The most in recent years, body lithium rechargeable battery and double layer capacitor combined System's research becomes new focus.
The carbon materials such as lithium-ion capacitor general anode material selection graphite, hard carbon, positive electrode selects electric double layer special The absorbent charcoal material of property, is carried out the pre-doping of lithium ion, makes negative pole current potential significantly decline, thus improve by anticathode material Energy density.Disclosing a kind of lithium-ion capacitor in patent CN200580001498.2, this lithium-ion capacitor uses Plus plate current-collecting body and negative current collector are respectively provided with the hole running through positive and negative, respectively by positive active material and negative electrode active material shape Become electrode layer, carry out electrochemical contact by anticathode, in advance lithium ion is carried in negative pole.Patent CN200780024069.6 discloses the preprocess method of a kind of electrochemical capacitor negative pole, by vapor phase method or liquid phase Method forms lithium layer on substrate, and then this lithium layer is transferred to the electrode layer of negative pole.The work that the method for these pre-doping relates to Skill is more complicated, and needs raw material to carry out special handling, brings certain difficulty to manufacture process.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of a kind of lithium ion super capacitor positive electrode, should Positive electrode prepared by method can provide lithium source in lithium-ion capacitor, carries out the pre-embedding of complexity from without anticathode again Lithium processes or adds lithium sheet in lithium-ion capacitor, simplifies technical process prepared by lithium-ion capacitor, reduces it Process costs.
The preparation method of the lithium ion super capacitor positive electrode that the present invention provides is:
Step (1) is by Li2CO3And MoO3The ratio mixing of 1-2:1, puts into Muffle furnace 500-700 after mix homogeneously in molar ratio DEG C reaction 3-8 hour, reaction terminate after obtain Li2MoO4Material.
Step (2) by graphite oxide with obtain Li2MoO4Material is mixed by quality 50-5:1, puts into after uniform mix homogeneously In the Muffle furnace of the hydrogen nitrogen mixed gas atmosphere protection containing 5% hydrogen, 500-900 DEG C is reacted 5-10 hour, and reaction obtains stone after terminating Ink alkene is combined Li2MoO3Material.
The present invention provides the preparation technology flow process of a kind of lithium ion super capacitor as follows:
(1) Graphene is combined Li2MoO3Material, conductive agent, binding agent join in NMP according to the ratio of mass ratio 90:5:5 It is mixed into slurry, is then coated with on plus plate current-collecting body aluminium foil, after drying, obtains positive plate.
(2) graphite or carbon cathode material, conductive agent, binding agent firmly are joined according to the ratio of mass ratio 90:5:5 NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(3) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
The lithium ion battery that the technique using positive electrode of the present invention to prepare lithium ion super capacitor is general prepares work Skill, enormously simplify the preparation technology of lithium ion super capacitor.
Graphene prepared by the present invention is combined Li2MoO3When material is used as lithium ion super capacitor positive electrode, Li2MoO3Material provides lithium source, the lithium ion abjection Li when initial charge2MoO3Material is inserted in graphite cathode, thus drags down Negative pole current potential, therefore need not in negative pole use metal lithium sheet or the pre-embedding lithium technique of complexity;Graphene is combined Li2MoO3Material Li in material2MoO3Support graphene film Rotating fields, effectively prevent grapheme material from reuniting and reducing specific surface area;Simultaneously Li2MoO3Material forms Li after sloughing lithium ion2-xMoO3Material is electrochemicaUy inert material, does not affect the normal use of battery.
There is advantages that (1) Graphene is combined Li2MoO3Material is as lithium ion super capacitor Positive pole makes negative pole need not add the pre-embedding lithium technique of lithium sheet or complexity, simplifies preparation technology, reduces cost;(2) Graphene is combined Li2MoO3Material has high connductivity, high-specific surface area can effectively substitute conventional activated carbon positive electrode, Realize high-energy-density and high power density.
Accompanying drawing explanation
Fig. 1 is the cycle life figure of ultracapacitor of the present invention.
Detailed description of the invention
Below in conjunction with the accompanying drawings, the preferably embodiment of the present invention is described in further detail:
Embodiment 1
(1) by Li2CO3And MoO3The ratio mixing of 1:1, puts into Muffle furnace 500 DEG C reaction 3 little after mix homogeneously in molar ratio Time, reaction obtains Li after terminating2MoO4Material.
(2) by graphite oxide with obtain Li2MoO4Material is mixed by quality 50:1, puts into containing 5% hydrogen after uniform mix homogeneously In the Muffle furnace of the hydrogen nitrogen mixed gas atmosphere protection of gas, 500 DEG C are reacted 5 hours, and reaction obtains Graphene after terminating and is combined Li2MoO3 Material.
(3) Graphene is combined Li2MoO3Material, conductive agent Ketjen black, binding agent PVDF are according to the ratio of mass ratio 90:5:5 Example joins and is mixed into slurry in NMP, is then coated with on plus plate current-collecting body aluminium foil, obtains positive plate after drying.
(4) graphite cathode material, conductive agent Ketjen black, binding agent PVDF are joined according to the ratio of mass ratio 90:5:5 NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(5) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
Embodiment 2
(1) by Li2CO3And MoO3The ratio mixing of 2:1, puts into Muffle furnace 700 DEG C reaction 8 little after mix homogeneously in molar ratio Time, reaction obtains Li after terminating2MoO4Material.
(2) by graphite oxide with obtain Li2MoO4Material is mixed by quality 5:1, puts into containing 5% hydrogen after uniform mix homogeneously Hydrogen nitrogen mixed gas atmosphere protection Muffle furnace in 900 DEG C react 10 hours, reaction obtains Graphene and is combined Li after terminating2MoO3 Material.
(3) Graphene is combined Li2MoO3Material, conductive agent Ketjen black, binding agent PVDF are according to the ratio of mass ratio 90:5:5 Example joins and is mixed into slurry in NMP, is then coated with on plus plate current-collecting body aluminium foil, obtains positive plate after drying.
(4) graphite cathode material, conductive agent Ketjen black, binding agent PVDF are joined according to the ratio of mass ratio 90:5:5 NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(5) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
Embodiment 3
(1) by Li2CO3And MoO3The ratio mixing of 1.3:1, puts into Muffle furnace 600 DEG C reaction 7 after mix homogeneously in molar ratio Hour, reaction obtains Li after terminating2MoO4Material.
(2) by graphite oxide with obtain Li2MoO4Material is mixed by quality 25:1, puts into containing 5% hydrogen after uniform mix homogeneously In the Muffle furnace of the hydrogen nitrogen mixed gas atmosphere protection of gas, 700 DEG C are reacted 8 hours, and reaction obtains Graphene after terminating and is combined Li2MoO3 Material.
(3) Graphene is combined Li2MoO3Material, conductive agent Ketjen black, binding agent PVDF are according to the ratio of mass ratio 90:5:5 Example joins and is mixed into slurry in NMP, is then coated with on plus plate current-collecting body aluminium foil, obtains positive plate after drying.
(4) hard carbon cathode material, conductive agent Ketjen black, binding agent PVDF are joined according to the ratio of mass ratio 90:5:5 NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(5) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
Embodiment 4
(1) by Li2CO3And MoO3The ratio mixing of 1.5:1, puts into Muffle furnace 650 DEG C reaction 5 after mix homogeneously in molar ratio Hour, reaction obtains Li after terminating2MoO4Material.
(2) by graphite oxide with obtain Li2MoO4Material is mixed by quality 15:1, puts into containing 5% hydrogen after uniform mix homogeneously In the Muffle furnace of the hydrogen nitrogen mixed gas atmosphere protection of gas, 600 DEG C are reacted 8 hours, and reaction obtains Graphene after terminating and is combined Li2MoO3 Material.
(3) Graphene is combined Li2MoO3Material, conductive agent Ketjen black, binding agent PVDF are according to the ratio of mass ratio 90:5:5 Example joins and is mixed into slurry in NMP, is then coated with on plus plate current-collecting body aluminium foil, obtains positive plate after drying.
(4) hard carbon cathode material, conductive agent Ketjen black, binding agent PVDF are joined according to the ratio of mass ratio 90:5:5 NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(5) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
Embodiment 5
(1) by Li2CO3And MoO3The ratio mixing of 1.7:1, puts into Muffle furnace 600 DEG C reaction 6 after mix homogeneously in molar ratio Hour, reaction obtains Li after terminating2MoO4Material.
(2) by graphite oxide with obtain Li2MoO4Material is mixed by quality 35:1, puts into containing 5% hydrogen after uniform mix homogeneously In the Muffle furnace of the hydrogen nitrogen mixed gas atmosphere protection of gas, 800 DEG C are reacted 6 hours, and reaction obtains Graphene after terminating and is combined Li2MoO3 Material.
(3) Graphene is combined Li2MoO3Material, conductive agent Ketjen black, binding agent PVDF are according to the ratio of mass ratio 90:5:5 Example joins and is mixed into slurry in NMP, is then coated with on plus plate current-collecting body aluminium foil, obtains positive plate after drying.
(4) graphite cathode material, conductive agent Ketjen black, binding agent PVDF are joined according to the ratio of mass ratio 90:5:5 NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(5) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
Its effect is as shown in table 1, as shown in Table 1: lithium ion super capacitor energy density prepared by the present invention reaches 38.8-46.1 wh/kg, has reached the fluence level of conventional lithium ion super capacitor.
As shown in Figure 1: lithium ion super capacitor discharge and recharge prepared by the present invention 1000 times, energy has no substantially decay.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Energy density (wh/kg) 44.6 38.8 43.6 42 46.1
Above content is to combine concrete preferred implementation further description made for the present invention, it is impossible to assert this Bright being embodied as is confined to these explanations.For general technical staff of the technical field of the invention, do not taking off On the premise of present inventive concept, it is also possible to make some simple deduction or replace, all should be considered as belonging to the protection of the present invention Scope.

Claims (10)

1. the preparation method of a lithium ion super capacitor positive electrode, it is characterised in that include that the following steps are rapid:
Step (1) is by Li2CO3And MoO3Mixing, puts into Muffle reaction in furnace after mix homogeneously, reaction obtains Li after terminating2MoO4 Material;
Step (2) by graphite oxide with obtain Li2MoO4Material mixing, puts into hydrogen nitrogen mixed gas atmosphere and protects after uniform mix homogeneously The Muffle reaction in furnace protected, reaction obtains Graphene after terminating and is combined Li2MoO3Material.
2. the method for claim 1, it is characterised in that Li in described step (1)2CO3And MoO3Amount 1-in molar ratio The ratio mixing of 2:1.
3. the method for claim 1, it is characterised in that the described step (1) reaction temperature in Muffle furnace is 500- 700 DEG C, the response time is 3-8 hour.
4. the method for claim 1, it is characterised in that in described step (2) graphite oxide with obtain Li2MoO4Material Quality in 50-5:1 ratio mix.
5. the method for claim 1, it is characterised in that in described step (2), the atmosphere in Muffle furnace is dense containing volume Spend the hydrogen nitrogen mixed gas of 5% hydrogen.
6. the method for claim 1, it is characterised in that the described step (2) reaction temperature in Muffle furnace is 500- 900 DEG C, the response time is 5-10 hour.
7. the preparation technology of a lithium ion super capacitor, it is characterised in that include following step:
Step A: the Graphene that such as claim 1 obtains is combined Li2MoO3Material, conductive agent, binding agent join in NMP mixed Synthetic slurry, is then coated with on plus plate current-collecting body aluminium foil, obtains positive plate after drying;
Step B: graphite or carbon cathode material, conductive agent, binding agent firmly are joined and is mixed into slurry in NMP, is then coated with On negative current collector Copper Foil paper tinsel, after drying, obtain negative plate;
Step C: negative plate, barrier film and positive plate are formed by the way of lamination according to the preparation technology of usual lithium ion battery Battery core, then injects electrolyte, sealing in battery case, obtains lithium ion super capacitor.
8. preparation technology as claimed in claim 7, it is characterised in that in described step A, Graphene is combined Li2MoO3Material, Conductive agent, the mass ratio of binding agent are 90:5:5.
9. preparation technology as claimed in claim 7, it is characterised in that in described step B, graphite or firmly carbon cathode material, Conductive agent, the mass ratio of binding agent are 90:5:5.
10. preparation technology as claimed in claim 7, it is characterised in that in described step C, described electrolyte is 1mol/L LiPF6DOL-DME solution, wherein, the volume ratio of DOL and DME is 1:1.
CN201610616219.3A 2016-07-31 2016-07-31 A kind of preparation method of lithium ion super capacitor grapheme composite positive electrode material Pending CN106098408A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106847520A (en) * 2016-12-22 2017-06-13 宁波中车新能源科技有限公司 A kind of lithium-ion capacitor positive pole and its application
WO2018023326A1 (en) * 2016-07-31 2018-02-08 肖丽芳 Method for preparing graphene composite cathode material of lithium ion supercapacitor

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CN103855373A (en) * 2012-11-30 2014-06-11 海洋王照明科技股份有限公司 Vanadium pentoxide / graphene composite material and its preparation method and application
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CN101165827A (en) * 2007-08-29 2008-04-23 李青海 Mixed electrochemical capacitor and its manufacture method
WO2012043398A1 (en) * 2010-09-29 2012-04-05 エスペック株式会社 Method for drying electrode pair, method for manufacturing lithium-ion secondary battery, method for manufacturing electric double-layer capacitor, and method for manufacturing lithium-ion capacitor
CN103326028A (en) * 2012-03-23 2013-09-25 株式会社半导体能源研究所 Power storage device and method for manufacturing the same
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Publication number Priority date Publication date Assignee Title
WO2018023326A1 (en) * 2016-07-31 2018-02-08 肖丽芳 Method for preparing graphene composite cathode material of lithium ion supercapacitor
CN106847520A (en) * 2016-12-22 2017-06-13 宁波中车新能源科技有限公司 A kind of lithium-ion capacitor positive pole and its application
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Application publication date: 20161109