CN106784898B - A kind of lithium and cobalt oxides and carbon black blending type catalyst and its preparation method and application - Google Patents
A kind of lithium and cobalt oxides and carbon black blending type catalyst and its preparation method and application Download PDFInfo
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- CN106784898B CN106784898B CN201710123474.9A CN201710123474A CN106784898B CN 106784898 B CN106784898 B CN 106784898B CN 201710123474 A CN201710123474 A CN 201710123474A CN 106784898 B CN106784898 B CN 106784898B
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- lithium
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- carbon black
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
Abstract
The present invention relates to a kind of lithium and cobalt oxides and carbon black blending type catalyst and preparation method thereof, which is solid powder, and the size of cobalt oxidate for lithium particle is less than or equal to 5 μm, and lithium and cobalt oxides and carbon black are blended uniform.It is to redox reactions catalytic activity with higher, in addition, the present invention provides, preparation method is easy, and cost is relatively low, easy to industrialized production and application oxygen reduction catalyst.The catalyst hydrogen reduction electro catalytic activity with higher and stability in alkaline medium.In addition to this, the present invention also develops the method that a kind of secondary cycle of discarded cobalt acid lithium utilizes, and alleviates environmental pollution and energy shortage problem.
Description
Technical field
The invention belongs to field of catalyst preparation, and in particular to a kind of lithium and cobalt oxides and carbon black blending type catalyst and its
Preparation method and application.The catalyst is to the electro catalytic activity with higher of oxygen reduction reaction in alkaline medium and durability.And
And after lithium removing, the oxygen reduction activities of oxide show the electricity extracted from discarded lithium ion battery there is no reducing
Pole material still has excellent oxygen reduction activities, can be used as lithium-air battery and fuel battery negative pole redox reactions
Catalyst, so that the recovery utilization rate of lithium ion battery greatly improves.
Background technique
In the practical application of novel energy battery fuel cell and metal-air battery, redox reactions (ORR)
It is a very important half-reaction.Redox reactions are related to multiple reaction steps and multiple transfer electronics, are a complexity
Reaction process.Due to the feature that its dynamics is slow, oxygen reduction catalyst is essential.The selection criteria needs of catalyst are examined
Consider the following aspects: catalytic activity, thermodynamic stability, corrosion resistance, price, long-time stability etc..It is most common
Oxygen reduction catalyst is business Pt/C, and this catalyst activity is preferable, but noble metal platinum scarcity of resources, expensive, valence
Lattice and durability limit its application.Therefore the catalyst for developing novel inexpensive, efficient, alternative Pt/C, which becomes, to be ground
The emphasis studied carefully.Studying more ORR catalyst now has Pt noble metal catalyst, transition metal macrocyclic compound, transition
Metal oxide, carbon material (carbon material).
Cobalt acid lithium is the common positive electrode of lithium ion battery, is six side's layer structures, and layer structure advantageously forms yin
The channel of pole removal lithium embedded, to complete charge and discharge process.And battery is by after several hundred secondary charge and discharge, electrode material can be because poor
Lithium is expanded, is shunk, and crystal form changes, and generates irreversible transition, is reduced the available capacity of anode, is led to its electrochemistry
Performance failure.The cobalt acid lithium of failure becomes solid refuse, not only pollutes the environment, but also will cause the waste of resource.If will
It is recycled, and obtains the cobalt acid lithium of poor lithium after treatment, i.e., the lithium and cobalt oxides of de- lithium improve itself and carbon black blending
Its electric conductivity is made catalyst and is applied to Cathodic oxygen reduction, is the effective use to stale resource, can also be in certain journey
The noble metal catalyst of resource scarcity is replaced on degree.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the present invention provides a kind of lithium and cobalt oxides and carbon black blending type
Catalyst and preparation method thereof, to redox reactions catalytic activity with higher, in addition, the present invention provides preparation method
Simplicity, cost is relatively low, easy to industrialized production and application oxygen reduction catalyst.The catalyst has higher in alkaline medium
Hydrogen reduction electro catalytic activity and stability.In addition to this, the present invention also develops a kind of secondary cycle benefit of discarded cobalt acid lithium
Method alleviates environmental pollution and energy shortage problem.
The present invention adopts the following technical scheme that, a kind of lithium and cobalt oxides and carbon black blending type catalyst, the catalyst are solid
Body powder, the size of cobalt oxidate for lithium particle are less than or equal to 5 μm, and lithium and cobalt oxides and carbon black are blended uniform.
Further, the lithium and cobalt oxides are business cobalt acid lithium or the de- lithium cobalt acid lithium by removing elemental lithium.
Lithium and cobalt oxides are blended with carbon black, can be used as the catalyst of lithium-air battery and fuel battery negative pole redox reactions.Even if
After removing lithium, there is no reduce for the oxygen reduction electro catalytic activity of blending type catalyst composed by oxide and carbon black.This
Kind lithium and cobalt oxides and carbon black blending type catalyst can be applied in the redox reactions of alkaline medium, improve cell cathode
The efficiency of reaction.
Further, the carbon black is one of Vulcan XC-72, ketjenblack EC, carbon nanotube, graphene
Or it is several.
Further, the blending ratio of the lithium and cobalt oxides and carbon black is 0.3:1 ~ 1:1.
Further, the de- lithium cobalt acid lithium is prepared using discarded cobalt acid lithium as raw material.
Further, the de- lithium cobalt acid lithium is prepared via a method which to obtain:
(1) organic solvent is added in a reservoir, is passed through inert gas, be then added in organic solvent discarded cobalt acid lithium and
Oxidant, the two is evenly dispersed in organic solvent, seals after continuously stirring 30 ~ 45min of reaction；
(2) it keeps after stirring 18 ~ 30h under conditions of sealing, is filtered, washed repeatedly with solvent, obtain being covered with sample
The filter paper of product, is put into baking oven and is dried, and drying temperature is 60 ~ 80 DEG C, and the time is 8 ~ 12h, obtains the lithium cobalt oxidation of de- lithium
Object.
Further, the oxidant is nitronium tetrafluoroborate, the abjection amount of lithium by oxidant nitronium tetrafluoroborate dosage
It determines, from the abjection process in positive electrode, cobalt acid lithium and nitronium tetrafluoroborate rub lithium in corresponding lithium ion battery charging process
You are than being 1:0.1 ~ 1:1.
Further, the solvent is anhydrous acetonitrile, and the inert gas is argon gas.
The present invention also protect the lithium and cobalt oxides with carbon black blending type catalyst answering in redox reactions catalyst
With.
Compared with prior art, the present invention is urged using lithium and cobalt oxides prepared by the method for chemical lithium deintercalation with carbon black blending type
Agent, with the increase of the abjection amount of lithium, so that crystal structure is gradually converted into cubic spinel structure from six side's layer structures.
The electric conductivity on the one hand improving lithium and cobalt oxides is blended with carbon black for the lithium and cobalt oxides of de- lithium, on the other hand improves its oxygen also
Former activity.Catalyst half wave potential in 0.1M KOH solution is 0.79V.The catalyst can be applied to metal-air battery
With the cathodic oxygen reduction catalyst of fuel cell.
In addition, even if after removing lithium, the oxygen reduction electro-catalysis of blending type catalyst composed by oxide and carbon black
There is no reduce for activity.This shows that the cobalt acid lithium electrode material extracted from discarded lithium ion battery still has excellent oxygen
Gas reduction activation can be used as the catalyst of lithium-air battery and fuel battery negative pole redox reactions, this is conducive to big at present
Measure the recycle and reuse of the lithium ion battery used.
Detailed description of the invention
The following further describes the present invention with reference to the drawings:
Fig. 1 is SEM and the TEM figure of catalyst obtained in embodiment 1；
Wherein figure a is TEM and the SEM figure of cobalt acid lithium,
Figure b is SEM and the TEM figure of the lithium and cobalt oxides prepared；
Fig. 2 is the XRD diagram of catalyst obtained in embodiment 1；
Fig. 3 is the Raman figure of catalyst obtained in embodiment 1；
Fig. 4 is that catalyst that cobalt acid lithium is blended with carbon black is obtained in embodiment 1 in the 0.1M KOH solution that oxygen is saturated
Polarization curve spectrogram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, without structure
At limitation of the present invention.
Embodiment 1:
Prepare lithium and cobalt oxides and carbon black blending type catalyst that lithium abjection amount is 90%.
(1) 15 ~ 45ml anhydrous acetonitrile is added in round-bottomed flask, is passed through argon gas, 100 ~ 300mg cobalt acid lithium and one is added
Determine the oxidant nitronium tetrafluoroborate of quality, the two is dispersed in anhydrous acetonitrile, is sealed after continuously stirring 30 ~ 45min of reaction；
(2) it keeps after stirring 18 ~ 30h under conditions of sealing, is filtered with vacuum filtration machine, with the anhydrous second of 50 ~ 200ml
Nitrile wash several times, obtain the filter paper for being covered with sample, be put into baking oven and be dried, drying temperature be 60 ~ 80 DEG C, the time be 8 ~
12h obtains the lithium and cobalt oxides of de- lithium；
(3) lithium and cobalt oxides are blended with carbon black, blending ratio is 0.3:1 ~ 1:1, obtains lithium and cobalt oxides and carbon black is total
Mixed type catalyst.
Fig. 1 is SEM and the TEM figure of catalyst obtained in embodiment 1, wherein figure a is TEM and the SEM figure of cobalt acid lithium, figure
B is SEM and the TEM figure of the lithium and cobalt oxides prepared, it can be seen from the figure that cobalt acid lithium and lithium and cobalt oxides grain shaped obtained
Shape is irregular, and for crystallite dimension at 5 μm or so, de- lithium makes crystallite dimension become smaller.Fig. 2 is catalyst obtained in embodiment 1
XRD diagram, the characteristic peak positions for as can be seen from the figure preparing raw materials used cobalt acid lithium are consistent with standard card, deviate from 90% lithium
Afterwards, characteristic peak positions determine the abjection of lithium closer to the characteristic peak of cobaltosic oxide, compared with standard card to the right slightly partially
It moves, illustrates that lithium is not yet all deviate from.Fig. 3 is the Raman figure of catalyst obtained in embodiment 1, it can be seen from the figure that abjection
Belong to the characteristic peak 486cm of cobalt acid lithium in the lithium and cobalt oxides Raman figure obtained after 90% lithium in cobalt acid lithium-1, 596cm-1Intensity
Weaken, in 679cm-1There is new characteristic peak, it is corresponding with the characteristic peak positions of cobaltosic oxide through comparing, but be slightly displaced from.Table
When bright lithium abjection amount is 90%, the crystal structure of lithium and cobalt oxides is via six original side's layer structures to cubic spinel knot
Allosteric transformation.Fig. 4 is the 0.1M that the catalyst that catalyst obtained in embodiment 1 and cobalt acid lithium are blended with carbon black is saturated in oxygen
Polarization curve spectrogram in KOH solution.Sweep speed is 5mv/s, and electrode rotary speed is 1600rpm, it can be seen from the figure that
Although the lithium and cobalt oxides after abjection lithium still differ more with the activity of business Pt/C, half wave potential differs 75 mv, in cost
Under the premise of reduction, preferable oxygen reduction catalytic activity is still kept.In addition, the lithium and cobalt oxides after de- lithium are lived compared with cobalt acid lithium
Property be not substantially reduced or even increase, half wave potential improves 14 mv, illustrate recycling waste lithium ion in lithium
Cobalt/cobalt oxide can be applied to hydrogen reduction electro-catalysis direction, be conducive to the protection of environment and the effective use of resource.
Embodiment 2:
Prepare lithium and cobalt oxides and carbon black blending type catalyst that lithium abjection amount is 50%.
(1) 15 ~ 45ml anhydrous acetonitrile is added in round-bottomed flask, is passed through argon gas, 100 ~ 300mg cobalt acid lithium and one is added
Determine the oxidant nitronium tetrafluoroborate of quality, the two is dispersed in anhydrous acetonitrile, is sealed after continuously stirring 30 ~ 45min of reaction；
(2) it keeps after stirring 18 ~ 30h under conditions of sealing, is filtered with vacuum filtration machine, with the anhydrous second of 50 ~ 200ml
Nitrile wash several times, obtain the filter paper for being covered with sample, be put into baking oven and be dried, drying temperature be 60 ~ 80 DEG C, the time be 8 ~
12h obtains the lithium and cobalt oxides of de- lithium；
(3) lithium and cobalt oxides are blended with carbon black, blending ratio is 0.3:1 ~ 1:1, obtains lithium and cobalt oxides and carbon black is total
Mixed type catalyst.
Schemed by the SEM and TEM of the lithium and cobalt oxides and carbon black blending type catalyst prepared, finds the catalysis prepared
The crystallite dimension of agent is at 5 μm or so, and the abjection of lithium is so that crystallite dimension becomes smaller.It can be seen that from XRD diagram, the abjection prepared
The lithium and cobalt oxides characteristic peak positions of 50% lithium, peak position relative intensity corresponding with cobalt acid lithium reduces, corresponding with cobaltosic oxide
Peak position relative intensity becomes strong, the intermediate state in the two, confirms the part abjection of lithium.It is opposite by characteristic peak from Raman figure
Strength Changes, it may be determined that the variation of the part abjection and crystal structure of lithium.From polarization curve, it may be determined that catalyst is to oxygen
The catalytic activity of reduction reaction.
Embodiment 3:
Prepare lithium and cobalt oxides and carbon black blending type catalyst that lithium abjection amount is 10%.
(1) 15 ~ 45ml anhydrous acetonitrile is added in round-bottomed flask, is passed through argon gas, 100 ~ 300mg cobalt acid lithium and one is added
Determine the oxidant nitronium tetrafluoroborate of quality, the two is dispersed in anhydrous acetonitrile, is sealed after continuously stirring 30 ~ 45min of reaction；
(2) it keeps after stirring 18 ~ 30h under conditions of sealing, is filtered with vacuum filtration machine, with the anhydrous second of 50 ~ 200ml
Nitrile wash several times, obtain the filter paper for being covered with sample, be put into baking oven and be dried, drying temperature be 60 ~ 80 DEG C, the time be 8 ~
12h obtains the lithium and cobalt oxides of de- lithium；
(3) lithium and cobalt oxides are blended with carbon black, blending ratio is 0.3:1 ~ 1:1, obtains lithium and cobalt oxides and carbon black is total
Mixed type catalyst.
Schemed by the SEM and TEM of the lithium and cobalt oxides and carbon black blending type catalyst prepared, finds the catalysis prepared
The crystallite dimension of agent is at 5 μm or so, and the abjection of lithium is so that crystallite dimension becomes smaller.It can be seen that from XRD diagram, the abjection prepared
The lithium and cobalt oxides characteristic peak positions of 10% lithium, peak position relative intensity corresponding with cobalt acid lithium reduces, corresponding with cobaltosic oxide
Peak position relative intensity becomes strong, the intermediate state in the two, confirms the part abjection of lithium.It is opposite by characteristic peak from Raman figure
Strength Changes, it may be determined that the variation of the part abjection and crystal structure of lithium.From polarization curve, it may be determined that catalyst is to oxygen
The catalytic activity of reduction reaction.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
The change or replacement expected without creative work, should be covered by the protection scope of the present invention.Therefore, of the invention
Protection scope should be determined by the scope of protection defined in the claims.
Claims (4)
1. a kind of lithium and cobalt oxides and carbon black blending type catalyst, which is characterized in that the catalyst is solid powder, and cobalt is lithium
The size of object particle is less than or equal to 5 μm, and lithium and cobalt oxides and carbon black are blended uniform；The lithium and cobalt oxides are by removing
The de- lithium cobalt acid lithium of elemental lithium；The carbon black is Vulcan XC-72, ketjenblack EC, carbon nanotube, one in graphene
Kind is several；The blending ratio of the lithium and cobalt oxides and carbon black is 0.3:1 ~ 1:1；The de- lithium cobalt acid lithium is to discard cobalt
Sour lithium is prepared for raw material；The de- lithium cobalt acid lithium is prepared via a method which to obtain:
(1) organic solvent is added in a reservoir, is passed through inert gas, discarded cobalt acid lithium and oxidation are then added in organic solvent
Agent, the two is evenly dispersed in organic solvent, seals after continuously stirring 30 ~ 45min of reaction；
(2) it keeps after stirring 18 ~ 30h under conditions of sealing, is filtered, washed repeatedly with solvent, obtain being covered with sample
Filter paper is put into baking oven and is dried, and drying temperature is 60 ~ 80 DEG C, and the time is 8 ~ 12h, obtains the lithium and cobalt oxides of de- lithium；
The oxidant is nitronium tetrafluoroborate.
2. catalyst according to claim 1, which is characterized in that cobalt acid lithium and the molar ratio of nitronium tetrafluoroborate be 1:0.1 ~
1:1。
3. catalyst according to claim 1, which is characterized in that the solvent is anhydrous acetonitrile, the indifferent gas
Body is argon gas.
4. lithium and cobalt oxides of any of claims 1-3 and carbon black blending type catalyst are catalyzed in redox reactions
The application of agent.
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| CN109802144B (en) * | 2019-02-02 | 2020-09-11 | 北京师范大学 | Atmosphere battery anode catalyst material and preparation method thereof |
| CN110526273A (en) * | 2019-09-02 | 2019-12-03 | 北京邮电大学 | A kind of method that the de- lithium of electrochemistry prepares high valence transition metal oxide-based nanomaterial |
Citations (3)
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| CN102307661A (en) * | 2009-02-09 | 2012-01-04 | 巴斯夫欧洲公司 | Hydrogenation catalysts, the production and the use thereof |
| CN104495811A (en) * | 2014-12-12 | 2015-04-08 | 盐城市新能源化学储能与动力电源研究中心 | Graphene composite material and preparation method thereof |
| CN105514468A (en) * | 2010-12-16 | 2016-04-20 | 24M技术公司 | High energy density redox flow device |
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| US7776776B2 (en) * | 2006-08-29 | 2010-08-17 | Chung Shan Institute Of Science And Technology, Armaments Bureau, M.N.D. | Method for preparing catalyst platinum supported on lithium cobalt oxide |
| US20090214417A1 (en) * | 2007-12-26 | 2009-08-27 | University Of Delaware | Preparation of cobalt-boron alloy catalysts useful for generating hydrogen from borohydrides |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102307661A (en) * | 2009-02-09 | 2012-01-04 | 巴斯夫欧洲公司 | Hydrogenation catalysts, the production and the use thereof |
| CN105514468A (en) * | 2010-12-16 | 2016-04-20 | 24M技术公司 | High energy density redox flow device |
| CN104495811A (en) * | 2014-12-12 | 2015-04-08 | 盐城市新能源化学储能与动力电源研究中心 | Graphene composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| LixCo3-xO4 solid solution nanocrystals supported on carbon black as a superior electrocatalyst for oxygen reduction reaction;Hongcan Liu et al;《Materials Letters》;20141104(第139期);447页右栏实验部分，448页左栏第二段，图1A，1B * |
| Nora Colligan et al.Evidence of Localized Lithium Removal in Layered and Lithiated Spinel Li1−xCoO2 (0 ≤ x ≤ 0.9) under Oxygen Evolution Reaction Conditions.《J. Phys. Chem. C》.2015,(第119期),2335-2340页. * |
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