CN107195463A - One kind contains Li2MoO3The preparation method of coating positive plate - Google Patents

One kind contains Li2MoO3The preparation method of coating positive plate Download PDF

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CN107195463A
CN107195463A CN201610619940.8A CN201610619940A CN107195463A CN 107195463 A CN107195463 A CN 107195463A CN 201610619940 A CN201610619940 A CN 201610619940A CN 107195463 A CN107195463 A CN 107195463A
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moo
positive plate
mixed
binding agent
conductive agent
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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
    • H01G11/04Hybrid capacitors
    • H01G11/06Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01G11/26Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • H01G11/84Processes 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)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provides a kind of containing Li2MoO3The preparation method of coating positive plate.Including following steps:Step(1)By Li2CO3And MoO3Mixing, is put into Muffle reaction in furnace after being well mixed, reaction obtains Li after terminating2MoO4Material;Step(2)Li will be obtained2MoO4The Muffle reaction in furnace of hydrogen nitrogen mixed gas atmosphere protection is put into, reaction obtains Li after terminating2MoO3Material;Step(3)By Li2MoO3Material, conductive agent, binding agent, which are added in NMP, is mixed into slurry, is then coated with containing active material positive plate, is obtained after drying containing Li2MoO3Coating positive plate.The present invention has the advantages that:(1)Contain Li2MoO3The positive plate of coating makes negative pole to add the pre- embedding lithium technique of lithium piece or complexity for the positive pole of lithium ion super capacitor, simplifies preparation technology, reduces cost.

Description

One kind contains Li2MoO3The preparation method of coating positive plate
Technical field
The invention belongs to lithium ion super capacitor technical field, it is related to a kind of system of lithium ion super capacitor positive plate Preparation Method.
Background technology
In recent years, lithium rechargeable battery has obtained very big development, and this GND is typically using the charcoals such as graphite element Material, positive pole contains lithium metal oxide using cobalt acid lithium, LiMn2O4 etc..After this battery pack is filled with, negative pole is to positive pole during charging Lithium ion is provided, and the lithium ion of positive pole returns to negative pole in electric discharge, therefore it is referred to as " rocking chair type battery ".With using metal The lithium battery of lithium is compared, the characteristics of this battery has high security and high circulation life-span.
But, due to the deformation of positive electrode easy recurring structure during removal lithium embedded, therefore, lithium ion secondary electricity The cycle life in pond is still restricted.Therefore in recent years, the body that lithium rechargeable battery and double layer capacitor are combined together System's research turns into new focus.
The carbon materials such as lithium-ion capacitor general anode material selection graphite, hard carbon, positive electrode is special from electric double layer Property absorbent charcoal material, by negative material carry out lithium ion pre-doping, negative pole current potential is significantly declined, so as to improve Energy density.A kind of lithium-ion capacitor is disclosed in patent CN200580001498.2, what this lithium-ion capacitor was used Plus plate current-collecting body and negative current collector are respectively provided with through the hole of positive and negative, respectively by positive active material and negative electrode active material shape Into electrode layer, by carrying out electrochemical contact to negative pole, lithium ion is carried in negative pole in advance.Patent A kind of preprocess method of electrochemical capacitor negative pole is disclosed in CN200780024069.6, passes through vapor phase method or liquid phase Method forms lithium layer on substrate, and then the lithium layer is transferred to the electrode layer of negative pole.The work that the method for these pre-doping is related to Skill is more complicated, and raw material are needed to carry out specially treated, and certain difficulty is brought to manufacturing process.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of lithium ion super capacitor positive plate, the party Positive plate prepared by method can provide lithium source in lithium-ion capacitor, without being carried out again to negative pole at complicated pre- embedding lithium Reason adds lithium piece in lithium-ion capacitor, simplifies the technical process of lithium-ion capacitor preparation, reduces its technique Cost.
The preparation method for the lithium ion super capacitor positive plate that the present invention is provided is:
Step(1)By Li2CO3And MoO31-2 in molar ratio:1 ratio mixing, 500-700 in Muffle furnace is put into after being well mixed DEG C reaction 3-8 hour, react terminate after obtain Li2MoO4Material.
Step(2)Li will be obtained2MoO4Material is put into the Muffle of the hydrogen nitrogen mixed gas atmosphere protection of the hydrogen containing volumetric concentration 5% 500-900 DEG C is reacted 5-10 hours in stove, and reaction obtains Li after terminating2MoO3Material.
Step(3)By Li2MoO3Material, conductive agent, binding agent are according to 80-90:5-10:5-10 mass ratio is added to Slurry is mixed into NMP, is then coated with containing active material positive plate, is obtained after drying containing Li2MoO3Coating positive pole Piece.
It is as follows that the present invention provides a kind of preparation technology flow of lithium ion super capacitor:
(1)By activated carbon or graphene anode material, conductive agent, binding agent according to 90:5:5 ratio is added in NMP and mixed Synthetic slurry, is then coated with plus plate current-collecting body aluminium foil, positive plate is obtained after drying.
(2)By Li2MoO3Material, conductive agent, binding agent are according to 80-90:5-10:5-10 mass ratio is added in NMP Slurry is mixed into, is then coated with containing active material positive plate, is obtained after drying containing Li2MoO3Coating positive plate.
(3)By graphite or hard charcoal negative material, conductive agent, binding agent according to mass ratio 90:5:5 ratio is added to Slurry is mixed into NMP, is then coated with negative current collector copper foil paper tinsel, negative plate is obtained after drying.
(4)According to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate the group by way of lamination Into battery core, electrolyte is then injected in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL Volume ratio with DME is 1:1), seal, obtain lithium ion super capacitor.
Use positive electrode of the present invention to prepare the technique of lithium ion super capacitor and prepare work for general lithium ion battery Skill, enormously simplify the preparation technology of lithium ion super capacitor.
Prepared by the present invention contains Li2MoO3When the positive plate of coating is used as lithium ion super capacitor positive electrode, Li2MoO3Material provides lithium source, and in initial charge, lithium ion deviates from Li2MoO3Material is inserted into graphite cathode, so as to drag down Negative pole current potential, therefore need not be using metal lithium sheet or the pre- embedding lithium technique of complexity in negative pole;While Li2MoO3Material is sloughed Li is formed after lithium ion2-xMoO3Material is electrochemicaUy inert material, does not influence the normal of battery to use.
The present invention has the advantages that:(1)Contain Li2MoO3The positive plate of coating is lithium ion super capacitor Positive pole makes negative pole to add the pre- embedding lithium technique of lithium piece or complexity, simplifies preparation technology, reduces cost.
Brief description of the drawings
Fig. 1 is lithium ion super capacitor positive plate structural representation of the present invention.
In figure, 1-plus plate current-collecting body, 2-active material positive plate, 3-Li2MoO3Coating.
Embodiment
Below in conjunction with the accompanying drawings, the preferably embodiment to the present invention is described in further detail:
Embodiment 1
(1)By Li2CO3And MoO3In molar ratio 1:1 ratio mixing, is put into 500 DEG C of reactions 3 in Muffle furnace small after being well mixed When, reaction obtains Li after terminating2MoO4
(2)Li will be obtained2MoO4It is put into the Muffle furnace containing volumetric concentration for the hydrogen nitrogen mixed gas atmosphere protection of 5% hydrogen 500 DEG C are reacted 5 hours, and reaction obtains Li after terminating2MoO3Material.
(3)By absorbent charcoal material, conductive agent Ketjen black, binding agent PVDF according to mass ratio 90:5:5 ratio is added to Slurry is mixed into NMP, is then coated with the aluminium foil of plus plate current-collecting body 1, positive plate is obtained after drying.
(4)By Li2MoO3Material, conductive agent Ketjen black, binding agent PVDF are according to mass ratio 80: 10:10 mass ratio It is added in NMP and is mixed into slurry, is then coated with containing active material positive plate 2, is obtained after drying containing Li2MoO3Apply 3 positive plate of layer.
(5)By graphite cathode material, conductive agent Ketjen black, binding agent PVDF according to mass ratio 90:5:5 ratio is added to Slurry is mixed into NMP, is then coated with negative current collector copper foil, negative plate is obtained after drying.
(6)According to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate the group by way of lamination Into battery core, electrolyte is then injected in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL Volume ratio with DME is 1:1), seal, obtain lithium ion super capacitor.
Embodiment 2
(1)By Li2CO3And MoO3In molar ratio 2:1 ratio mixing, is put into 700 DEG C of reactions 8 in Muffle furnace small after being well mixed When, reaction obtains Li after terminating2MoO4
(2)Li will be obtained2MoO4It is put into the Muffle furnace containing volumetric concentration for the hydrogen nitrogen mixed gas atmosphere protection of 5% hydrogen 900 DEG C are reacted 10 hours, and reaction obtains Li after terminating2MoO3Material.
(3)By absorbent charcoal material, conductive agent, binding agent according to mass ratio 90:5:5 ratio, which is added in NMP, to be mixed into Slurry, is then coated with the aluminium foil of plus plate current-collecting body 1, positive plate is obtained after drying.
(4)By Li2MoO3Material, conductive agent Ketjen black, binding agent PVDF are according to mass ratio 90:5:5 mass ratio is added Slurry is mixed into NMP, is then coated with containing active material positive plate 2, is obtained after drying containing Li2MoO3Coating 3 is just Pole piece.
(5)By hard charcoal negative material, conductive agent Ketjen black, binding agent PVDF according to mass ratio 90:5:5 ratio is added to Slurry is mixed into NMP, is then coated with negative current collector copper foil paper tinsel, negative plate is obtained after drying.
(6)According to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate the group by way of lamination Into battery core, electrolyte is then injected in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL Volume ratio with DME is 1:1), seal, obtain lithium ion super capacitor.
Embodiment 3
(1)By Li2CO3And MoO3In molar ratio 1.3:1 ratio mixing, is put into 600 DEG C of reactions 7 in Muffle furnace after being well mixed Hour, reaction obtains Li after terminating2MoO4
(2)Li will be obtained2MoO4It is put into 700 in the Muffle furnace of the hydrogen nitrogen mixed gas atmosphere protection of the hydrogen containing volumetric concentration 5% DEG C reaction 8 hours, reaction terminate after obtain Li2MoO3Material.
(3)By absorbent charcoal material, conductive agent Ketjen black, binding agent PVDF according to mass ratio 90:5:5 ratio is added to Slurry is mixed into NMP, is then coated with the aluminium foil of plus plate current-collecting body 1, positive plate is obtained after drying.
(4)By Li2MoO3Material, conductive agent Ketjen black, binding agent PVDF are according to 85:7:8 mass ratio is added to NMP In be mixed into slurry, be then coated with containing active material positive plate 2, obtained after drying containing Li2MoO3The positive plate of coating 3.
(5)By graphite cathode material, conductive agent Ketjen black, binding agent PVDF according to mass ratio 90:5:5 ratio is added to Slurry is mixed into NMP, is then coated with negative current collector copper foil, negative plate is obtained after drying.
(6)According to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate the group by way of lamination Into battery core, electrolyte is then injected in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL Volume ratio with DME is 1:1), seal, obtain lithium ion super capacitor.
Embodiment 4
(1)By Li2CO3And MoO3In molar ratio 1.5:1 ratio mixing, is put into 650 DEG C of reactions 5 in Muffle furnace after being well mixed Hour, reaction obtains Li after terminating2MoO4
(2)Li will be obtained2MoO4It is put into the Muffle furnace containing volumetric concentration for the hydrogen nitrogen mixed gas atmosphere protection of 5% hydrogen 600 DEG C are reacted 8 hours, and reaction obtains Li after terminating2MoO3Material.
(3)By absorbent charcoal material, conductive agent Ketjen black, binding agent PVDF according to 90:5:5 ratio is added in NMP and mixed Synthetic slurry, is then coated with the aluminium foil of plus plate current-collecting body 1, positive plate is obtained after drying.
(4)By Li2MoO3Material, conductive agent Ketjen black, binding agent PVDF are according to 82:9:9 mass ratio is added to NMP In be mixed into slurry, be then coated with containing active material positive plate 2, obtained after drying containing Li2MoO3The positive plate of coating 3.
(5)By hard charcoal negative material, conductive agent Ketjen black, binding agent PVDF according to mass ratio 90:5:5 ratio is added to Slurry is mixed into NMP, is then coated with negative current collector copper foil, negative plate is obtained after drying.
(6)According to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate the group by way of lamination Into battery core, electrolyte is then injected in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL Volume ratio with DME is 1:1), seal, obtain lithium ion super capacitor.
Embodiment 5
(1)By Li2CO3And MoO3In molar ratio 1.7:1 ratio mixing, is put into 600 DEG C of reactions 6 in Muffle furnace after being well mixed Hour, reaction obtains Li after terminating2MoO4
(2)Li will be obtained2MoO4It is put into the Muffle furnace containing volumetric concentration for the hydrogen nitrogen mixed gas atmosphere protection of 5% hydrogen 800 DEG C are reacted 6 hours, and reaction obtains Li after terminating2MoO3Material.
(3)By absorbent charcoal material, conductive agent Ketjen black, binding agent PVDF according to mass ratio 90:5:5 ratio is added to Slurry is mixed into NMP, is then coated with the aluminium foil of plus plate current-collecting body 1, positive plate is obtained after drying.
(4)By Li2MoO3Material, conductive agent Ketjen black, binding agent PVDF are according to 88:6:6 mass ratio is added to NMP In be mixed into slurry, be then coated with containing active material positive plate 2, obtained after drying containing Li2MoO3The positive plate of coating 3.
(5)By graphite cathode material, conductive agent Ketjen black, binding agent PVDF according to mass ratio 90:5:5 ratio is added to Slurry is mixed into NMP, is then coated with negative current collector copper foil, negative plate is obtained after drying.
(6)According to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate the group by way of lamination Into battery core, electrolyte is then injected in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL Volume ratio with DME is 1:1), seal, 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 34.6-37.1 wh/kg, have reached the fluence level of conventional lithium ion super capacitor.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Energy density(wh/kg) 35.2 36.6 37.1 34.8 34.6
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert this hair Bright specific implementation is confined to these explanations.For general technical staff of the technical field of the invention, do not taking off On the premise of from present inventive concept, some simple deduction or replace can also be made, the protection of the present invention should be all considered as belonging to Scope.

Claims (10)

1. a kind of preparation method of lithium ion super capacitor positive plate, it is characterised in that including following steps:
Step(1)By Li2CO3And MoO3Mixing, is put into Muffle reaction in furnace after being well mixed, reaction obtains Li after terminating2MoO4 Material;
Step(2)Li will be obtained2MoO4Material is put into the Muffle reaction in furnace of hydrogen nitrogen mixed gas atmosphere protection, and reaction is obtained after terminating To Li2MoO3Material;
Step(3)By Li2MoO3Material, conductive agent, binding agent, which are added in NMP, is mixed into slurry, is then coated with containing active On material positive plate, obtained after drying containing Li2MoO3Coating positive plate.
2. the method as described in claim 1, it is characterised in that the step(1)Middle Li2CO3And MoO3Amount 1- in molar ratio 2:1 ratio mixing.
3. the method as described in claim 1, it is characterised in that the step(1)Reaction temperature in Muffle furnace is 500- 700 DEG C, the reaction time is 3-8 hours.
4. the method as described in claim 1, it is characterised in that the step(2)Atmosphere in middle Muffle furnace is containing 5% hydrogen Hydrogen nitrogen mixed gas.
5. the method as described in claim 1, it is characterised in that the step(2)Reaction temperature in Muffle furnace is 500- 900 DEG C, the reaction time is 5-10 hours.
6. the method as described in claim 1, it is characterised in that the step(3)Middle Li2MoO3Material, conductive agent, binding agent Mass ratio be 80-90:5-10:5-10.
7. a kind of preparation technology of lithium ion super capacitor, it is characterised in that including following steps:
Step A:Activated carbon or graphene anode material, conductive agent and binding agent are added in NMP and are mixed into slurry, then It is coated on plus plate current-collecting body aluminium foil, positive plate is obtained after drying;
Step B:By the Li as prepared by claim 12MoO3Material, conductive agent, binding agent, which are added in NMP, is mixed into slurry, It is then coated with containing active material positive plate, is obtained after drying containing Li2MoO3Coating positive plate;
Step C:Graphite or hard charcoal negative material, conductive agent, binding agent are added in NMP and are mixed into slurry, is then coated with On negative current collector copper foil paper tinsel, negative plate is obtained after drying;
Step D:Negative plate, barrier film and positive plate are constituted into battery core by way of lamination, electrolysis is then injected in battery case Liquid, sealing, obtains lithium ion super capacitor.
8. preparation technology as claimed in claim 7, it is characterised in that in the 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 the step B, graphite or hard charcoal negative 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 the step C, the electrolyte is 1mol/L LiPF6DOL-DME solution, wherein, DOL and DME volume ratio is 1:1.
CN201610619940.8A 2016-07-31 2016-07-31 One kind contains Li2MoO3The preparation method of coating positive plate Pending CN107195463A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109935831A (en) * 2017-12-18 2019-06-25 上海纳晓能源科技有限公司 Electrode inertness material, combination electrode, production method and lithium ion battery

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Publication number Priority date Publication date Assignee Title
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
CN103515110A (en) * 2012-06-26 2014-01-15 海洋王照明科技股份有限公司 Li2MoO3/graphene composite material, preparing method thereof and lithium ion capacitor
CN104577088A (en) * 2013-10-16 2015-04-29 中国科学院物理研究所 Lithium molybdate serving as secondary battery electrode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103515110A (en) * 2012-06-26 2014-01-15 海洋王照明科技股份有限公司 Li2MoO3/graphene composite material, preparing method thereof and lithium ion capacitor
CN104577088A (en) * 2013-10-16 2015-04-29 中国科学院物理研究所 Lithium molybdate serving as secondary battery electrode material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109935831A (en) * 2017-12-18 2019-06-25 上海纳晓能源科技有限公司 Electrode inertness material, combination electrode, production method and lithium ion battery

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Application publication date: 20170922