CN108172844A - A kind of lithium air battery positive electrode material preparation method and lithium-air battery - Google Patents
A kind of lithium air battery positive electrode material preparation method and lithium-air battery Download PDFInfo
- Publication number
- CN108172844A CN108172844A CN201810097792.7A CN201810097792A CN108172844A CN 108172844 A CN108172844 A CN 108172844A CN 201810097792 A CN201810097792 A CN 201810097792A CN 108172844 A CN108172844 A CN 108172844A
- Authority
- CN
- China
- Prior art keywords
- lithium
- air battery
- positive electrode
- presoma
- foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M4/8605—Porous electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
The invention belongs to electrochemical energy source domain more particularly to a kind of lithium air battery positive electrode material preparation methods and lithium-air battery.Utilize Co made from water-heat process3O4@Ni nano-wire arrays have larger specific surface area, cause the porous structure of nano wire and ideal specific surface using the process of low temperature calcination, increase the contact area of electrolyte and electrode, more reactivity sites are provided for ORR and OER processes.After immersion treatment, nanowire surface is roughening, and coarse surface so that the specific surface area of nano wire is increased, and provides the memory space of more discharging products.And after impregnating, Co3O4It is reduced, Lacking oxygen and surface defect increase, and active site increases, conducive to the reversible formation of the weak crystal form film-form discharging product of catalyst surface is promoted with decomposing so that the overall performance of lithium-air battery is obviously improved.
Description
Technical field
The invention belongs to electrochemical energy source domain more particularly to a kind of lithium air battery positive electrode material preparation method and lithium are empty
Pneumoelectric pond.
Background technology
Lithium-air battery has the energy density of superelevation, is 6-9 times of lithium ion battery, almost with conventional fossil fuel vapour
Oil phase is worked as, and is expected to the major impetus source as novel electric vehicle, therefore as research hotspot both domestic and external.
Lithium-air battery using lithium metal as cathode, porous diffusion layer is air cathode, in discharge process by lithium with
The chemical energy of oxygen is transformed into electric energy, and by decomposing the discharging product (Li of non-aqueous system during charging2O2And water
LiOH in system) store electric energy.Since the insolubility and insulating properties of discharging product lead to its irreversible decomposition and decomposition
Not exclusively, poor invertibity and cyclical stability are eventually led to.
In lithium-air battery, carbon material is due to conductive height, oxygen adsorption capacity is strong, oxygen reduction activity is good, cost
Low characteristic and the preparation for being widely used as positive electrode, common are carbon black, mesoporous carbon, carbon nanotube, carbon fiber and graphene
Deng.However, carbon material can promote electrolyte decomposition to generate Li in discharge process2CO3And LiRCO3Wait by-products, charging process
Middle Li2CO3Decomposition can cause charging voltage to be more than 4V, while when more than 3.5V, carbon material also easily decomposes, so as to reduce library
Human relations efficiency influences battery performance.
Therefore, using metal as substrate, the self-cradling type non-carbon positive electrode that transition metal oxide makees catalyst gradually goes out
Everybody visual field now.But current non-carbon positive electrode, while by-product is reduced, transition metal oxide is poor
Electric conductivity again limits the discharge process of lithium-air battery, influences the overall performance of battery.
Invention content
The present invention provides a kind of lithium air battery positive electrode material preparation method and lithium-air battery, it is intended to solve existing lithium
Air cell non-carbon positive conductive is poor, limit the discharge process of lithium-air battery, and the overall performance for influencing battery is asked
Topic.
A kind of lithium air battery positive electrode material preparation method provided by the invention, the method includes：
Co is grown in foam nickel base using hydro-thermal reaction3O4Presoma；
To the Co3O4Presoma is calcined, and makes the Co3O4Presoma is converted into Co3O4, obtain Ni load Cs o3O4；
By the Ni load Cs o3O4It is soaked in NaBH4It in solution, is cleaned, is dried with deionized water after taking-up, obtained
Lithium-air battery non-carbon positive electrode.
Further, Co is grown in foam nickel base using hydro-thermal reaction described3O4Before presoma, the method
It further includes：Foam nickel material is pre-processed, obtains the nickel foam；It specifically includes：
The foam nickel material is cut into pre-set dimension, merging organic solvent for ultrasonic impregnates 3-10min, uses deionization
It after water rinses, is placed in the HCl solution of a concentration of 1-10mol/L and is cleaned by ultrasonic 10-30min, rinsed, done with ethyl alcohol, water successively
Dry processing obtains the nickel foam.
Further, it is described that Co is grown in foam nickel base using hydro-thermal reaction3O4Presoma specifically includes：
Co salt and urea are dissolved in the water, obtain Co2+The solution one of a concentration of 0.075-0.1mol/L, wherein, Co salt
Molar ratio with urea is 1:2-8；
The solution one is placed in reaction kettle, and is put into the nickel foam as substrate in the reaction kettle, is sealed,
4-10h is kept at 80-150 DEG C；
Reaction kettle described in natural cooling takes out the nickel foam, is cleaned by ultrasonic 2-3 times with water, and drying obtains the Co3O4
Presoma.
Further, it is described to the Co3O4Presoma is calcined, and makes the Co3O4Presoma is converted into Co3O4, obtain
Obtain Ni load Cs o3O4It specifically includes：
Load there is into the Co3O4The nickel foam of presoma is calcined at 200-500 DEG C, keeps the temperature 2-4h；The heating
Rate is 3-5 DEG C/min.5th, it is according to the method described in claim 1, it is characterized in that, described by the Ni load Cs o3O4It impregnates
In NaBH4It in solution, is cleaned, is dried with deionized water after taking-up, obtained lithium-air battery non-carbon positive electrode and specifically wrap
It includes：
By the Ni load Cs o3O4It is soaked in NaBH4In solution, soaking time 0.5-4h.After taking-up, deionized water is used
Cleaning 4-5 times is placed in 60 DEG C of oven dryings, obtains lithium-air battery non-carbon positive electrode.The NaBH4Solution concentration is 0.3-
1.2mol/L。
The present invention also provides a kind of lithium-air batteries, described just extremely to adopt including anode, cathode, diaphragm and electrolyte
The lithium-air battery non-carbon positive electrode made of above-mentioned lithium air battery positive electrode material preparation method.
Lithium air battery positive electrode material preparation method provided by the invention obtains Ni load Cs o3O4(Co at this time3O4It can shape
Into nano wire, i.e. Co3O4@Ni nano wires), Co made from water-heat process3O4@Ni nano-wire arrays have larger specific surface area,
The porous structure of nano wire and ideal specific surface are caused using the process of low temperature calcination, increases connecing for electrolyte and electrode
Contacting surface is accumulated, and more reactivity sites are provided for ORR and OER processes.After immersion treatment, nanowire surface is roughening,
Coarse surface so that the specific surface area of nano wire is increased, and provides the memory space of more discharging products.And impregnate it
Afterwards, Co3O4It is reduced, Lacking oxygen and surface defect increase, and active site increases, conducive to the weak crystal form of catalyst surface is promoted
The reversible formation of film-form discharging product is with decomposing so that the overall performance of lithium-air battery is obviously improved.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention.
Fig. 1 is a kind of lithium air battery positive electrode material preparation method flow chart provided in an embodiment of the present invention；
Fig. 2 is a kind of another flow chart of lithium air battery positive electrode material preparation method provided in an embodiment of the present invention；
Fig. 3 is the details of step 102 in a kind of lithium air battery positive electrode material preparation method provided in an embodiment of the present invention
Flow chart；
Fig. 4 is non-carbon positive electrode Co in the embodiment of the present invention 13O4@Ni (load C o3O4Foam nickel electrode) FESEM
Figure；
Fig. 5 is non-carbon positive electrode r-Co in the embodiment of the present invention 23O4@Ni (the Co being reduced by immersion treatment3O4@
Ni electrodes) FESEM figure；
Fig. 6 is non-carbon positive electrode r-Co in the embodiment of the present invention 23O4The TEM figures of@Ni；
Fig. 7 is without using r-Co3O4The r- that@Ni are provided by the lithium-air battery and use the present embodiment of anode
Co3O4@Ni are voltage-capacity comparison diagram of the lithium-air battery of anode under the conditions of current density is 50mA/g；
Fig. 8 is non-carbon positive electrode Co in the embodiment of the present invention 13O4@Ni lithium-air batteries are 200mA/g in current density
Under the conditions of capacitance-voltage cycle figure；
Fig. 9 is non-carbon positive electrode r-Co in the embodiment of the present invention 23O4@Ni lithium-air batteries are 200mA/ in current density
Capacitance-voltage cycle figure under the conditions of g；
Figure 10 is without using r-Co3O4The r- that@Ni are provided by the lithium-air battery and use the present embodiment of anode
Co3O4@Ni are charging voltage-cycle comparison diagram of the lithium-air battery of anode under the conditions of current density is 200mA/g.
Specific embodiment
In order to make the invention's purpose, features and advantages of the invention more obvious and easy to understand, below in conjunction with the present invention
The technical solution in the embodiment of the present invention is clearly and completely described in attached drawing in embodiment, it is clear that described reality
It is only part of the embodiment of the present invention to apply example, and not all embodiments.Based on the embodiments of the present invention, people in the art
Member's all other embodiments obtained without making creative work, shall fall within the protection scope of the present invention.
Fig. 1 is please referred to, Fig. 1 is a kind of lithium air battery positive electrode material preparation method flow provided in an embodiment of the present invention
Figure, this method include：
Step 101：Co is grown in foam nickel base using hydro-thermal reaction3O4Presoma.
Step 102：To Co3O4Presoma is calcined, and makes the Co3O4Presoma is converted into Co3O4, obtain Ni loads
Co3O4(it is Co3O4@Ni non-carbon positive electrode).
Step 103：By the Ni load Cs o3O4It is soaked in NaBH4It in solution, cleaned after taking-up with deionized water, dry place
Reason, it (is r-Co to obtain lithium-air battery non-carbon positive electrode3O4@Ni non-carbon positive electrode).
Lithium air battery positive electrode material preparation method provided by the invention, is grown by water-heat process and low temperature calcination
In the Co in foam nickel base3O4Presoma is converted into Co3O4, obtain Ni load Cs o3O4(Co at this time3O4Nano wire can be formed,
That is Co3O4@Ni nano wires), then use NaBH4Solution is to Co3O4It is restored, you can obtain lithium-air battery non-carbon anode material
Material.Co made from water-heat process3O4@Ni nano-wire arrays have larger specific surface area, are caused using the process of low temperature calcination
The porous structure of nano wire and ideal specific surface increase the contact area of electrolyte and electrode, are that (oxygen reduction is anti-by ORR
Should) and OER (oxygen evolution reaction) process provide more reactivity sites.In addition, after immersion treatment, nanowire surface becomes
Coarse, although whole pattern is not substantially change, coarse surface so that the specific surface area of nano wire is increased, and provides
The memory space of more discharging products.And after impregnating, Co3O4It is reduced, Lacking oxygen and surface defect increase, catalytic active site
Point increases, conducive to the reversible formation of the weak crystal form film-form discharging product of catalyst surface is promoted with decomposing so that lithium-air battery
Overall performance be obviously improved.
As shown in figure 3, step 101 specifically comprises the following steps：
Step 201：Co salt and urea are dissolved in the water, obtain Co2+The solution one of a concentration of 0.075-0.1mol/L,
In, the molar ratio of Co salt and urea is 1:2-8 (preferably 1:3-4).
Step 202：The solution one is placed in reaction kettle, and the reaction kettle is put into using the nickel foam as substrate
In, sealing is placed under 80-150 DEG C (preferably 100-120 DEG C) and keeps 4-10h (preferably 6-8h).
Step 203：Reaction kettle described in natural cooling takes out nickel foam, is cleaned by ultrasonic 2-3 times with water, drying, described in acquisition
Co3O4Presoma.
In step 102：Load there is into the Co3O4The nickel foam of presoma is calcined at 200-500 DEG C, preferably 300-
400 DEG C, most preferably using 350 DEG C of low temperature, keep the temperature 2-4h, preferably 2-3h；The rate control of the heating in 1-7 DEG C/min,
Preferably 3-5 DEG C/min.
During above-mentioned steps 101 and 102, Co that water-heat process obtains3O4Presoma is subcarbonate, in high temperature ring
It is reacted under border with oxygen, crystalline transition Co3O4While release CO2And vapor, construct a large amount of of nano-array surface
It is mesoporous so that specific surface area increases, and obtains Co3O4@Ni non-carbon positive electrodes.
In step 103：By the Ni load Cs o3O4It is soaked in NaBH4In solution, soaking time 0.5-4h, preferably
0.5-2h.It after taking-up, is cleaned 4-5 times with deionized water, is placed in 60 DEG C of oven dryings, obtain lithium-air battery non-carbon anode material
Material.Wherein NaBH4Solution concentration is 0.3-1.2mol/L, preferably 0.5-1mol/L.
During above-mentioned steps 103, mainly to Co in soaking process3O4It is restored, and is produced with a small amount of hydrogen
It is raw, target product is made：R-Co with Lacking oxygen3O4@Ni electrodes.Wherein, the load capacity of catalyst is equal to most on positive electrode
The quality of whole target product subtracts blank nickel foam NaBH4Quality after solution treatment.Finally, according to the model of lithium-air battery
(such as：Button CR2032) it is cut into the positive electrode pole piece of a diameter of 1.5cm disc-shapeds.The cutting of lithium-air battery pole piece is used
Manual sheet-punching machine is completed, and when carrying out punching to cathode sheet, in cathode sheet both sides, clean paper covers, to prevent
Only the impurity contamination on sheet-punching machine is polluted in positive electrode on piece.Cathode sheet is protected under dry room temperature environment
It deposits.
As shown in Fig. 2, before step 101, further include step 104：Foam nickel material is pre-processed, obtains foam
Nickel.It specifically includes：
According to actual conditions needs, foam nickel material is cut into pre-set dimension, merging organic solvent for ultrasonic impregnates 3-
10min, preferably 5-7min after being rinsed with deionized water, are placed in the HCl solution of a concentration of 1-10mol/L (preferably 3-6M)
Middle ultrasonic cleaning 10-30min, preferably 15-20min are rinsed with ethyl alcohol, water, are dried, obtain the nickel foam successively.
In conclusion the lithium air battery positive electrode material preparation method provided using above-described embodiment 1, the lithium prepared
The total load amount of air non-carbon cell positive material is 1-1.2mg/cm2。
The present invention also provides a kind of lithium-air battery, including anode, cathode, diaphragm and electrolyte, it is described just extremely on
The lithium air battery positive electrode material stated.
The open-circuit voltage of lithium-air battery provided in this embodiment ranging from 2.95V~3.20V.Keeping charge and discharge specific volume
It measures as 300mAh/g, voltage range 2-4.55V, under conditions of current density is 200mA/g, the cycle performance of the battery reaches
162 times.Compared to pure Co3O4@Ni electrodes, using r-Co3O4The lithium-air battery charge and discharge overpotential maximum drop of@Ni electrodes
Low 430mV or so effectively reduces the charging overpotential of lithium-air battery.
Embodiment 1
The preprocessing process of nickel foam is：Untreated nickel foam is cut into 3.2*5cm2Rectangular pieces, be placed in acetone
Ultrasound 5min removes surface and oil contaminant in solution, and deionized water uses the HCl of 3M to be cleaned by ultrasonic 15min removal Surface Oxygens after repeatedly rinsing
Compound.Then it is rinsed 3-5 times with absolute ethyl alcohol, deionized water successively, is placed in dried for standby in baking oven.
The preparation process of positive electrode is：
Co (the NO of 0.8731g are weighed successively3)2·6H2The urea (12mmol) of O (3mmol) and 0.72g is placed in 100mL's
In clean beaker, 40mL deionized waters are poured into, magnetic agitation is completely dissolved up to raw material, solution pinkiness.Solution is shifted
To reaction kettles of the 50mL with polytetrafluoroethyllining lining, the nickel foam rectangular pieces of above-mentioned dried for standby are put along the inner wall of liner
It puts, locks reaction kettle.
Reaction kettle is placed in 100-120 DEG C of baking oven and keeps the temperature 6h.Reaction kettle natural cooling is treated after hydro-thermal, is taken out negative
The nickel foam of presoma has been carried, has been rinsed 3-5 times with absolute ethyl alcohol and deionized water successively, 60 DEG C of dryings of baking oven.Before having loaded
The nickel foam for driving body is placed in tube furnace, and 2h is kept the temperature under conditions of air atmosphere, 350 DEG C, and heating rate is 3 DEG C/min.
According to the model (button CR2032) of lithium-air battery, the pole piece is cut into using manual sheet-punching machine a diameter of
The disk of 1.5cm is saved backup under dry room temperature environment.The pole piece load capacity is 1-1.2mg/cm2。
That embodiment 1 obtains is non-carbon positive electrode Co3O4@Ni, SEM morphology characterizations and TEM figures are respectively such as Fig. 4 and Fig. 6
It is shown.Low temperature calcination process causes presoma to be reacted with oxygen under air environment, generates Co3O4Metal aoxidizes and generates vapor
And carbon dioxide, form Co3O4The porous structure of nano-array.Gained cathode sheet is used to prepare lithium-air battery, with gold
Belong to lithium piece as cathode, 1M LiTFSI/TEGDME are electrolyte, prepare lithium-air battery, it is carried out in the environment of pure oxygen
The charge-discharge test of discharge capacity is not limited, as shown in figure 8, being 300mAh/g keeping charging and discharging capacity, current density is
Under conditions of 200mA/g, cycle performance is only 47 circles.
Embodiment 2
The preprocessing process of nickel foam is：Untreated nickel foam is cut into 3.2*5cm2Rectangular pieces, be placed in acetone
Ultrasound 5min removes surface and oil contaminant in solution, and deionized water uses the HCl of 3M to be cleaned by ultrasonic 15min removal Surface Oxygens after repeatedly rinsing
Compound.Then it is rinsed 3-5 times with absolute ethyl alcohol, deionized water successively, is placed in dried for standby in baking oven.
The preparation process of positive electrode is as follows：
The first step, water-heat process make to grow Co in foam nickel base3O4Presoma：
Co (the NO of 0.8731g are weighed successively3)2·6H2The urea (12mmol) of O (3mmol) and 0.72g is placed in 100mL's
In clean beaker, 40mL deionized waters are poured into, magnetic agitation is completely dissolved up to raw material, solution pinkiness.Solution is shifted
To reaction kettles of the 50mL with polytetrafluoroethyllining lining, the nickel foam rectangular pieces of dried for standby are placed along the inner wall of liner, locking
Reaction kettle.Reaction kettle is placed in 100-120 DEG C of baking oven and keeps the temperature 6h.Reaction kettle natural cooling is treated after hydro-thermal, takes out load
The nickel foam of presoma is rinsed 3-5 times, baking oven 60 DEG C of dryings with absolute ethyl alcohol and deionized water successively.
Second step, low temperature calcination under air atmosphere so that presoma is converted into Co3O4：
The nickel foam for having loaded presoma is placed in tube furnace, the lower 350 DEG C of heat preservations 2h of air atmosphere, heating rate 3
℃/min.Low temperature calcination process causes presoma to be reacted with oxygen under air environment, generates Co3O4Metal aoxidizes and generates water steaming
Gas and carbon dioxide, cause Co3O4The porous structure of nano-array, obtains Co3O4The non-carbon positive electrode of@Ni.
Third walks, by Co3O4@Ni electrodes are soaked in NaBH4In solution：
The NaBH of a concentration of 1mol/L of 30mL is configured4Solution, by Co3O4@Ni electrodes impregnate 1h as wherein.Soaking process
In mainly to Co3O4It is restored, constructs Lacking oxygen, and generate with a small amount of hydrogen,
4th step rinses drying, forms non-carbon positive electrode r-Co3O4@Ni：
The electrode after impregnating is taken out, and deionized water is rinsed 4-5 times, and dry 12h is placed in 60 DEG C of baking oven.Target is made
Product r-Co3O4@Ni electrodes.
That embodiment 2 obtains is non-carbon positive electrode r-Co3O4@Ni, SEM morphology characterizations are as shown in Figure 5.By gained just
Pole material piece is used to prepare lithium-air battery, and using metal lithium sheet as cathode, 1M LiTFSI/TEGDME are electrolyte, in pure oxygen
In the environment of do not limited it the charge-discharge test of discharge capacity, using positive electrode used as pure Co3O4@Ni, other groups
Into battery, Fig. 7 are without using r- as a comparison case with the identical lithium-air battery of the lithium-air battery of the present embodiment
Co3O4The r-Co that@Ni are provided by the lithium-air battery (i.e. above-mentioned comparative example battery) and use the present embodiment of anode3O4@Ni are
Deep discharge test result comparison diagram of the lithium-air battery of anode under 50mA/g current density conditions, compared to pure
Co3O4@Ni lithium-air batteries, using r-Co3O4@Ni as the lithium-air battery of air cathode material charge and discharge overpotential most
430mV or so is reduced greatly, effectively reduces the charging overpotential of lithium-air battery, and discharge capacity improves a lot.
Holding charging and discharging capacity is 300mAh/g, and under conditions of current density is 200mA/g, cycle performance reaches 162 times, is higher than
Co3O4Three times of@Ni, capacitance-voltage cycle figure is as shown in Figure 8 and Figure 9.Charging voltage in cyclic process is also substantially reduced,
Final pressure-cycle the figure that charges is as shown in Figure 10.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of lithium air battery positive electrode material preparation method, which is characterized in that the method includes：
Co is grown in foam nickel base using hydro-thermal reaction3O4Presoma；
To the Co3O4Presoma is calcined, and makes the Co3O4Presoma is converted into Co3O4, obtain Ni load Cs o3O4；
By the Ni load Cs o3O4It is soaked in NaBH4It in solution, is cleaned, is dried with deionized water after taking-up, it is empty to obtain lithium
Pneumoelectric pond non-carbon positive electrode.
2. it according to the method described in claim 1, it is characterized in that, is grown in foam nickel base using hydro-thermal reaction described
Co3O4Before presoma, the method further includes：Foam nickel material is pre-processed, obtains the nickel foam；It specifically includes：
The foam nickel material is cut into pre-set dimension, merging organic solvent for ultrasonic is impregnated 3-10min, rushed with deionized water
It after washing, is placed in the HCl solution of a concentration of 1-10mol/L and is cleaned by ultrasonic 10-30min, rinsed successively with ethyl alcohol, water, at drying
Reason, obtains the nickel foam.
3. according to the method described in claim 1, it is characterized in that, described grown using hydro-thermal reaction in foam nickel base
Co3O4Presoma specifically includes：
Co salt and urea are dissolved in the water, obtain Co2+The solution one of a concentration of 0.075-0.1mol/L, wherein, Co salt and urine
The molar ratio of element is 1:2-8；
The solution one is placed in reaction kettle, and is put into the nickel foam as substrate in the reaction kettle, is sealed,
4-10h is kept at 80-150 DEG C；
Reaction kettle described in natural cooling takes out the nickel foam, is cleaned by ultrasonic 2-3 times with water, and drying obtains the Co3O4Forerunner
Body.
It is 4. according to the method described in claim 1, it is characterized in that, described to the Co3O4Presoma is calcined, and is made described
Co3O4Presoma is converted into Co3O4, obtain Ni load Cs o3O4It specifically includes：
Load there is into the Co3O4The nickel foam of presoma is calcined at 200-500 DEG C, keeps the temperature 2-4h；The rate of the heating
For 3-5 DEG C/min.
It is 5. according to the method described in claim 1, it is characterized in that, described by the Ni load Cs o3O4It is soaked in NaBH4Solution
In, it is cleaned, is dried with deionized water after taking-up, obtained lithium-air battery non-carbon positive electrode and specifically include：
By the Ni load Cs o3O4It is soaked in NaBH4In solution, soaking time 0.5-4h.After taking-up, cleaned with deionized water
4-5 times, 60 DEG C of oven dryings are placed in, obtain lithium-air battery non-carbon positive electrode.
6. the according to the method described in claim 1, it is characterized in that, NaBH4Solution concentration is 0.3-1.2mol/L.
7. a kind of lithium-air battery, including anode, cathode, diaphragm and electrolyte, which is characterized in that described just extremely to use right
It is required that lithium-air battery non-carbon positive electrode made of lithium air battery positive electrode material preparation method described in 1 to 6 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810097792.7A CN108172844A (en) | 2018-01-31 | 2018-01-31 | A kind of lithium air battery positive electrode material preparation method and lithium-air battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810097792.7A CN108172844A (en) | 2018-01-31 | 2018-01-31 | A kind of lithium air battery positive electrode material preparation method and lithium-air battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108172844A true CN108172844A (en) | 2018-06-15 |
Family
ID=62512475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810097792.7A Pending CN108172844A (en) | 2018-01-31 | 2018-01-31 | A kind of lithium air battery positive electrode material preparation method and lithium-air battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108172844A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108977827A (en) * | 2018-08-01 | 2018-12-11 | 兰州大学 | Include FeSe2-Co3O4Composite material and preparation method and catalyst and application |
| CN109437328A (en) * | 2018-08-28 | 2019-03-08 | 五邑大学 | Preparation method of nano-scale short rod-shaped porous cobaltosic oxide electrode material |
| CN109560294A (en) * | 2018-11-30 | 2019-04-02 | 深圳大学 | A kind of lithium oxygen battery positive electrode and preparation method thereof and lithium oxygen battery |
| CN109802093A (en) * | 2019-01-21 | 2019-05-24 | 深圳大学 | Modified non-carbon anode of lithium-air battery and preparation method thereof and lithium-air battery |
| CN109904567A (en) * | 2019-02-20 | 2019-06-18 | 深圳大学 | Lithium-air battery and preparation method |
| CN110137511A (en) * | 2019-05-10 | 2019-08-16 | 深圳大学 | Y-oxides doping lithium air battery positive electrode and preparation method thereof and lithium-air battery |
| CN110548514A (en) * | 2019-08-07 | 2019-12-10 | 广东工业大学 | Hierarchical porous cobalt/iron bimetallic oxide nanosheet catalyst with rich oxygen vacancies and preparation method and application thereof |
| CN110828816A (en) * | 2019-09-29 | 2020-02-21 | 中国科学院大学 | Method for preparing oxygen vacancy lithium-rich manganese-based layered cathode material by solid-liquid method |
| CN113562774A (en) * | 2021-07-22 | 2021-10-29 | 辽宁大学 | Cathode material of zinc-cobalt battery rich in anion defects, preparation method of cathode material and application of cathode material to zinc-cobalt battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105332003A (en) * | 2015-11-30 | 2016-02-17 | 天津理工大学 | Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies |
| CN106732649A (en) * | 2017-02-20 | 2017-05-31 | 天津理工大学 | A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst |
-
2018
- 2018-01-31 CN CN201810097792.7A patent/CN108172844A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105332003A (en) * | 2015-11-30 | 2016-02-17 | 天津理工大学 | Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies |
| CN106732649A (en) * | 2017-02-20 | 2017-05-31 | 天津理工大学 | A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst |
Non-Patent Citations (1)
| Title |
|---|
| YONGCHENG WANG等: ""Reduced Mesoporous Co3O4 Nanowires as Efficient Water Oxidation Electrocatalysts and Supercapacitor Electrodes"", 《ADV. ENERGY MATER》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108977827A (en) * | 2018-08-01 | 2018-12-11 | 兰州大学 | Include FeSe2-Co3O4Composite material and preparation method and catalyst and application |
| CN108977827B (en) * | 2018-08-01 | 2020-08-28 | 兰州大学 | Comprising FeSe2-Co3O4Composite material and preparation method thereof, catalyst and application |
| CN109437328A (en) * | 2018-08-28 | 2019-03-08 | 五邑大学 | Preparation method of nano-scale short rod-shaped porous cobaltosic oxide electrode material |
| CN109560294A (en) * | 2018-11-30 | 2019-04-02 | 深圳大学 | A kind of lithium oxygen battery positive electrode and preparation method thereof and lithium oxygen battery |
| CN109802093A (en) * | 2019-01-21 | 2019-05-24 | 深圳大学 | Modified non-carbon anode of lithium-air battery and preparation method thereof and lithium-air battery |
| CN109904567A (en) * | 2019-02-20 | 2019-06-18 | 深圳大学 | Lithium-air battery and preparation method |
| CN110137511A (en) * | 2019-05-10 | 2019-08-16 | 深圳大学 | Y-oxides doping lithium air battery positive electrode and preparation method thereof and lithium-air battery |
| CN110548514A (en) * | 2019-08-07 | 2019-12-10 | 广东工业大学 | Hierarchical porous cobalt/iron bimetallic oxide nanosheet catalyst with rich oxygen vacancies and preparation method and application thereof |
| CN110548514B (en) * | 2019-08-07 | 2022-07-12 | 广东工业大学 | Hierarchical porous cobalt/iron bimetallic oxide nanosheet catalyst with rich oxygen vacancies and preparation method and application thereof |
| CN110828816A (en) * | 2019-09-29 | 2020-02-21 | 中国科学院大学 | Method for preparing oxygen vacancy lithium-rich manganese-based layered cathode material by solid-liquid method |
| CN113562774A (en) * | 2021-07-22 | 2021-10-29 | 辽宁大学 | Cathode material of zinc-cobalt battery rich in anion defects, preparation method of cathode material and application of cathode material to zinc-cobalt battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108172844A (en) | A kind of lithium air battery positive electrode material preparation method and lithium-air battery | |
| CN106876828B (en) | A kind of preparation method of lithium-air battery non-carbon anode, lithium-air battery | |
| CN107492452A (en) | The preparation method of array-like multilevel hierarchy cobalt sulfide nickel/nickel foam electrode of super capacitor | |
| CN105742658B (en) | The preparation method of electrode material for all-vanadium flow battery | |
| CN111029160B (en) | Zinc-cobalt double-metal selenide nanosheet electrode and preparation method thereof | |
| CN108682815A (en) | A kind of efficient hard carbon material and its preparation method and application | |
| CN109650493B (en) | VS with hierarchical structure2Synthesis method of nanosheet array electrode material | |
| CN107799756B (en) | Na2Ti3O7Preparation method of-C nano fiber | |
| CN107502919A (en) | A kind of sulfur doping catalyst of phosphatizing nickel for Hydrogen evolving reaction and preparation method thereof | |
| CN105529471A (en) | Treatment method for all-vanadium redox flow battery electrode | |
| CN107244664A (en) | The preparation method and application of class graphene-structured carbon electrode material | |
| CN109671575A (en) | A kind of preparation method of cobalt oxide manganese nano flower-carbon sponge flexible composite | |
| CN110223851A (en) | A kind of method of electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material | |
| CN108539203A (en) | Super hydrophilic material（Graphene oxide/phytic acid）Electrode material for modifying energy storage flow battery | |
| CN108123141A (en) | A kind of three-dimensional porous foams grapheme material and its application | |
| CN107634223A (en) | A kind of preparation method of Carbon negative electrode material of sodium ion battery | |
| JP2020059917A (en) | Tricobalt tetroxide array/titanium mesh electrode for water decomposition oxygen evolution and manufacturing method thereof | |
| CN111663152A (en) | Preparation method and application of foam nickel-loaded amorphous phosphorus-doped nickel molybdate bifunctional electrocatalytic electrode | |
| CN110137511A (en) | Y-oxides doping lithium air battery positive electrode and preparation method thereof and lithium-air battery | |
| CN106384674A (en) | Aqueous rechargeable sodium-ion capacitor battery based on titanium phosphorus oxide cathode material | |
| CN104134548B (en) | Porous composite material of manganese dioxide and carbon and preparation method thereof | |
| CN106356203B (en) | A kind of cobalt acid nickel nano film/graphite felt composite material and its preparation and application | |
| Ishihara et al. | Rechargeable lithium-air battery using mesoporous Co3O4 modified with Pd for air electrode | |
| CN107492451A (en) | The preparation method of loose structure cobalt acid zinc graphene composite active material/nickel foam electrode of super capacitor | |
| CN111509243A (en) | Application of CNTs modified BiOCl/ZnO heterojunction nano-array photo-anode in photocatalytic fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180615 |
|
| RJ01 | Rejection of invention patent application after publication |