CN104425803B - Method for preparing composite electrode material, composite electrode material and battery - Google Patents
Method for preparing composite electrode material, composite electrode material and battery Download PDFInfo
- Publication number
- CN104425803B CN104425803B CN201410072989.7A CN201410072989A CN104425803B CN 104425803 B CN104425803 B CN 104425803B CN 201410072989 A CN201410072989 A CN 201410072989A CN 104425803 B CN104425803 B CN 104425803B
- Authority
- CN
- China
- Prior art keywords
- hair
- electrode material
- ion
- preparation
- combination electrode
- 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.)
- Active
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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a composite electrode material. The method comprises the following steps: activating hair, dispersing the hair in a dispersing medium, and adding a metal source solution for soaking so as to adsorb metal ions; and calcining the hair in an oxygen-containing atmosphere or an inert atmosphere, thereby obtaining the composite electrode material containing metal oxides or metal sulfides. The invention also discloses a composite electrode material prepared by the preparation method and a battery containing the composite electrode material. According to the method disclosed by the invention, the process is simple and flexible, and complicated and accurate process control is not needed. According to the method disclosed by the invention, the hair serves as a biological template, the hair resources are rich and readily available, hair residues and other wastes can be effectively utilized, wastes are changed into valuable materials, and the cost is low. According to the method disclosed by the invention, lots of chemical reagents are not needed, the method is environment-friendly, and sustainable development of the environment is promoted.
Description
Technical field
The present invention relates to a kind of preparation method of combination electrode material.
The present invention relates to the combination electrode material that a kind of above-mentioned preparation method is obtained.
The present invention relates to a kind of battery including above-mentioned combination electrode material.
Background technology
In the past twenty years, the performance of rechargeable battery has very big improvement.Rechargeable battery can provide height
Energy density and power, this makes it be widely used in the fields such as hybrid vehicle, electric automobile and extensive energy storage.
But, the performance of rechargeable battery, cost and the sustainable development to environment remain that people are of interest to be asked
Topic.In general, in the constituent of rechargeable battery, electrode material in occupation of most important status, electrode pole material
Quality, directly affects the performance indications of final rechargeable battery.The cost of electrode material, is also to affect rechargeable battery cost
Key factor.
At present, the preparation method of existing electrode material, mostly chemical synthesis process.Such as coprecipitation, high temperature solid-state are closed
The methods such as Cheng Fa, hydro-thermal method, sol-gal process, microwave process for synthesizing.These synthetic methods are substantially more expensive and are unfavorable for environment
Sustainable development.
Nano-electrode material becomes the focus of the electrode material of people's research rechargeable battery due to excellent performance.When adopting
When synthesizing nano-electrode material with above-mentioned preparation method, complexity is generally required and accurate technology controlling and process.
The content of the invention
The technical problem to be solved is, the preparation method high cost of existing electrode material, synthesis technique be complicated,
And it is unfavorable for the sustainable development of environment.
The invention provides a kind of preparation method of combination electrode material, the preparation method includes：By hair and activation
Agent contact activates hair；Hair after activation is dispersed in decentralized medium, source metal solution is subsequently adding and is soaked to adsorb
Metal ion, then the hair after adsorbing metal ions is calcined under oxygen-containing atmosphere or inert atmosphere, obtain being aoxidized containing metal
The combination electrode material of thing or metal sulfide.
Preferably, the hair and activating agent are that hair is immersed in activator.
Preferably, the activator is NaOH or lithium hydroxide.
Preferably, the concentration of the activator is 0.1～1mol/L.
Preferably, the time of the activation is 1～24h.
Preferably, methods described is additionally included in the prerinse step before activation；The prerinse step is included hair
Wash in cleaning agent.
Preferably, the time of the washing is 15～60 minutes.
Preferably, the cleaning agent includes degreasing agent, and the degreasing agent is selected from ethanol, acetone, hexane, ethylenediamine tetra-acetic acid
With the one kind in dodecyl sodium sulfate.
Preferably, the cleaning agent includes foreign metal remover, and the foreign metal remover is selected from nitric acid and/or chlorine
Change iron.
Preferably, the mass percentage concentration of the nitric acid is 0.5～2%.
Preferably, the decentralized medium is ethyl acetate.
Preferably, the metal ion in the source metal solution selected from magnesium ion, copper ion, manganese ion, cobalt ions, nickel from
One or more in son, iron ion and aluminium ion.
Preferably, the anion in the source metal solution selected from sulfate ion, nitrate ion, acetate ion and
One or more in acetoacetate radical ion.
Preferably, in adsorbing metal ions, the number of times of the immersion is at least twice；And it is soaked twice adjacent
Between, hair is leached from source metal solution.
Preferably, in adsorbing metal ions, the time of immersion is 2～24h.
Preferably, in adsorbing metal ions, the pH value of the solution of immersion is 8～9.
Preferably, the temperature of the calcining is 600～900 DEG C.
Preferably, the time of the calcining is 2～8h.
Present invention also offers a kind of combination electrode material, the combination electrode material is by preparation provided by the present invention
Method is obtained.
Present invention also offers a kind of battery, the battery contains combination electrode material provided by the present invention.
Compared with prior art, preparation method of the invention, its process is simple is flexible, it is not necessary to complicated and accurate technique
Control.The preparation method of the present invention, using hair as biological template, hair aboundresources and easily acquisition, energy effectively utilizes
Hair slag the like waste, turns waste into wealth, with low cost.The preparation method of the present invention, should not use a large amount of chemical reagent, green ring
Protect, be conducive to the sustainable development of environment.
Description of the drawings
Fig. 1 (a) is schemed without the SEM of the hair of any process.
Fig. 1 (b) is the SEM figures of the hair after NaOH activation.
Fig. 1 (c) is the SEM figures for soaking the hair after source metal solution.
Fig. 1 (d) is the SEM figures for soaking the hair after washing after source metal solution.
Fig. 2 (a), 2 (b) are respectively SEM figures of the combination electrode material A1 under different amplification.
Fig. 3 (a), 3 (b) are respectively SEM figures of the combination electrode material A2 under different amplification.
Fig. 4 is the XRD of combination electrode material A1.
Fig. 5 is the cyclic voltammetry curve of combination electrode material A1 and A2.
Fig. 6 (a) is the voltage curve of combination electrode material A1.
Fig. 6 (b) is the voltage curve of combination electrode material A2.
Fig. 7 is cycle performance figure under lithium ion battery 0.1C made by combination electrode material A1.
Fig. 8 is the XRD of combination electrode material A3.
Fig. 9 is the voltage-specific capacity curve of lithium ion battery made by combination electrode material A3.
Figure 10 is the XRD of combination electrode material A4.
Figure 11 is the voltage-specific capacity curve of lithium ion battery made by combination electrode material A4.
Figure 12 (a), 12 (b) are SEM figures of the combination electrode material A5 under different amplification.
Figure 13 is the XRD of combination electrode material A5.
Figure 14 is the charging and discharging curve of lithium ion battery made by combination electrode material A5.
Figure 15 is the cycle performance figure of lithium ion battery made by combination electrode material A5.
Specific embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention, is not intended to limit the present invention.
A kind of preparation method of combination electrode material, the preparation method includes：Hair is set to live hair and activating agent
Change；Hair after activation is dispersed in decentralized medium, source metal solution is subsequently adding and is soaked with adsorbing metal ions, then will be inhaled
Hair after attached metal ion is calcined under oxygen-containing atmosphere or inert atmosphere, obtains containing metal oxide or metal sulfide
Combination electrode material.
The preparation method of combination electrode material of the present invention, using hair as biological template, is synthesized by biomineralization
Combination electrode material with special construction performance.
Wherein, metal oxide can be the oxide, or metal composite oxide of single metal.Equally, gold
Category sulfide can be the sulfide, or composition metal sulfide of single metal.
Hair is a kind of elongated, wire the product produced in skin follicle by mammal.The diameter of hair is about
For 50～100 μm.The main component of hair is alpha-Keratin.Hair is in turn divided into from inside to outside medullary substance, cutin according to form
Layer and epidermal area.Medullary substance is located at the center of hair；Cuticula is located at the outside of medullary substance, is by many tiny cellulosic groups of cells
Into；Epidermal area is located at cuticular outside, and by pinacocyte flakey is overlapping into.
The hair collected from places such as barber shops typically also contains grease, dust and other pollutants（For example have hair dyed
Agent, hair conditioner etc.）.Importantly, also containing some micro foreign metal ions in hair itself（Such as calcium ion）, this
A little foreign metal ions will affect the performance of the combination electrode material of final synthesis.
The species of the hair that collection is obtained, its component and component, content are often different.For example in different hairs
Melanin content, fat content, hair dyeing agent content etc. are variant.These factors can also affect the combination electrode material of final synthesis
Material performance.
Directly adopt untreated hair, the combination electrode material performance of final synthesis slightly have because hair is different difference, one
Cause property is poor.In order to eliminate the difference of the hair that different channels are collected, in order to improve the performance of the combination electrode material of synthesis
Uniformity, the present invention preferably hair activation before, increase prerinse step.
For the ease of prerinse and subsequent treatment, elongated hair can be cut into segment；Can not certainly segment.
The present invention is preferably cut into the segment of 2～6cm length.
Prerinse step includes hair is immersed in cleaning agent cleans, with remove the grease of hair surface, dust and
Other pollutants.
Preferably, cleaning agent includes degreasing agent and foreign metal remover.So pollutant can be more preferably removed, be improved
The chemical property and its consistency of final synthesis combination electrode material.
Wherein, the purpose of degreasing agent is to remove grease, the dust of hair surface.
Preferably, the one kind of degreasing agent in ethanol, acetone, hexane, ethylenediamine tetra-acetic acid and dodecyl sodium sulfate
Or it is several.
It is highly preferred that the degreasing agent is ethanol.
Wherein, the purpose of foreign metal remover is to remove other impurities metal ion in hair removal.
Foreign metal remover is selected from nitric acid or iron chloride.
Preferably, the mass percentage concentration of foreign metal remover is 0.5～2%.
It is further preferred that salpeter solution of the foreign metal remover for 1wt%.
Hair after the salpeter solution of 1wt% is processed, greatly reduces containing for impurity calcium sulfate in combination electrode material
Amount, effectively increases the performance of combination electrode material.
Additionally, foreign metal remover can also open the disulfide bond of cystine, and cystine be normally at it is many in hair
Between peptide chain.The opening of disulfide bond, can make metal cation more easily be diffused into an axle region of hair, make answering for synthesis
The micro-pipe of composite electrode material has thicker tube wall.
The prewashed time, the present invention is preferably at 15～60 minutes.
Under a preferred embodiment, prerinse includes, hair is first washed 30 minutes in ethanol, after exist again
Wash 30 minutes in the salpeter solution of 0.25mol/L.
By the hair after prerinse, activate in immersion activator.
The purpose of activation is the site of the water for opening the contact of hair mesocuticle surface.
Preferably, activator is selected from NaOH, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, disodium-hydrogen
With one or more in potassium phosphate,monobasic.
It is further preferred that activator is selected from NaOH and/or lithium hydroxide.
Preferably, the concentration of the activator is 0.1～1mol/L；More preferably 0.1～0.5mol/L.
As such, it is possible to make hair fully activate, strengthen the combination of hair and metal ion, and metal ion is on hair
Adsorbance, while the part scale tissue disappearance or damaged of hair surface can also be avoided；The portion in hair can also be avoided
There is basic hydrolysis in subangle albumen.
Preferably, the time of activation is 1～24h；More preferably 4h.
The abundant activation of hair is so may insure, the absorption property of metal ion is improved.
After the activation, wash away and be dried after activator.
Under a preferred embodiment, cleaned with substantial amounts of deionized water, until the pH value of cleaning fluid reaches 8～9, then
2～4h is dried at 110 DEG C.
Then, by the hair after activation in decentralized medium adsorbing metal ions.
The effect of decentralized medium is, bonding state of the fixing metal ions in hair surface.
Preferably, decentralized medium of the invention is selected from ethanol or ethyl acetate.
Stable absorption metal ion on hair can be very good using ethanol and ethyl acetate, metal ion is improved in hair
Deliver the bonding state in face.
Source metal solution can be the aqueous solution, or organic solution, present invention preferably employs the aqueous solution.
Metal ion in source metal solution, can be various transition metal ions and the portion in combination electrode material
Divide main group metal ion（Such as Group IIA, Group IIIA metal ion）.
Preferably, the metal ion in source metal solution selected from magnesium ion, copper ion, manganese ion, cobalt ions, nickel ion,
One or more in iron ion and aluminium ion.
Anion in source metal solution, as long as not affecting existence of the metal ion in source metal solution.
Such as chlorion, sulfate ion, nitrate ion, acetate ion, acetoacetate radical ion, formate ion, phosphate radical
Ion etc..
Preferably, the anion in source metal solution is selected from sulfate ion, nitrate ion, acetate ion and acetyl
One or more in acetate ion.
Wherein, immersion can once soak, it is also possible to soak by several times.
Once immersion refers to, the hair after activation is immersed in source metal solution once, and contains in source metal solution
All of metal ion in combination electrode material, once immersion reaches the purpose that metal ion all adsorbs.Once soak, both may be used
Suitable for synthesizing single metal oxide or single metal sulfide, can be applicable to synthesize metal composite oxide or multiple
Close metal sulfide.
To synthesize M1M2……MiComposite oxides as a example by illustrate, it is by M that it once soaks1、M2……MiIt is configured to gold
In the solution of category source, then the hair after activation is immersed in the source metal solution.
By several times immersion refers to, the hair after activation is successively repeatedly immersed in source metal solution, complete by several times metal from
The purpose of son absorption.I.e. by several times the immersion number of times of immersion at least twice, and it is adjacent soak twice between, by hair from source metal
Leach in solution.Equally, by several times immersion both goes for synthesizing single metal oxide or single metal sulfide, can be with
Suitable for synthesizing metal composite oxide or composition metal sulfide.
For synthesis metal composite oxide or composition metal sulfide, it is preferred to use soak by several times.
When soaking by several times, every time the source metal solution of immersion can be that identical, or source metal solution are different.
When each immersion source metal solution simultaneously, it is molten that the hair after will activating successively is immersed in identical source metal
In liquid.Hair after will activating first is immersed in a period of time in source metal solution, then leaches washing, then carries out second leaching
Bubble.
When being soaked using different source metal solution, can be species of metal ion in source metal solution it is different and/
Or concentration is different.
Wherein it is possible to be each immersion source metal solution in species of metal ion it is different, and every time containing only one kind, i.e.,
Only adsorb a metal ion species every time.To synthesize M1M2……MiComposite oxides as a example by illustrate, the hair elder generation after will activating
It is immersed in M1In source metal solution, then hair is separated, then the hair separated is immersed in into M2Source metal solution
In, then hair separated again ..., so until i ＆ lt, by hair M is immersed iniIn source metal solution.
Can also be that the species of metal ion in each source metal solution is different, and every time species number be it is indefinite,
Can be it is a kind of, two kinds or more kinds of.I.e. every time different metal ions are adsorbed in immersion.To synthesize M1M2……MiIt is compound
Illustrate as a example by oxide, the hair after will activating first is immersed in source metal solution（The M containing M1 ...x, in 1≤x≤i-1, then
Hair is separated, then the hair separated is immersed in into source metal solution（Containing Mx+1……My,x+1≤y≤i）
In ...
Certainly, each source metal solution can also contain part identical metal ion.
Include metal composite oxide or during composition metal sulfide when combination electrode material is synthesized, i.e. combination electrode material
In containing two kinds or during two or more metals, immersion by several times is preferably, every time the source metal metal ion in solution of immersion
Species it is different, so as to arrive the purpose of absorption different metal ions every time.
Preferably, according to the combination electrode material of synthesis, the pH of system solution can be adjusted to into 8～9 in immersion.So
The binding site that adsorbing metal ions can be avoided is protonated, so as to enhance the absorption of metal ion.
Preferably, the 2～24h of time of the immersion.So can ensure that metal ion is fully adsorbed onto on hair, improve
The performance of combination electrode material.
Preferably, the immersion is preferably carried out at room temperature.Soak at this temperature, be more beneficial for the suction of metal ion
It is attached, the combination electrode material excellent performance of synthesis.
Under a preferred embodiment, the present invention is ultrasonically treated in immersion process.
Immersion finish after, hair is separated from decentralized medium and source metal solution, and clean up with removal do not tie
The metal ion of conjunction；Then it is dried, to remove moisture removal.
Under a preferred embodiment, hair is leached from decentralized medium and source metal solution, then deionized water
Flush three times, then be dried to constant weight at 110 DEG C.
Preferred is soaked by several times after last time immersion is finished, namely after all immersions are finished, hair is cleaned
Totally；Only hair need to be separated from decentralized medium and source metal solution between soaking by several times, it is not necessary to clean up.This
Sample can effectively prevent the metal ion for adsorbing, and rinse from hair again in cleaning.
Hair after adsorbing metal ions, is put in calcining furnace and calcines.After calcining, metal ion is converted into metal
Oxide or metal sulfide, hair is changed into graphitic carbon.
According to the difference of the final combination electrode material for needing and synthesizing, the present invention can select to calcine under an oxygen-containing atmosphere,
Or calcine under an inert atmosphere.
When synthesis combination electrode material main component is oxide, composite oxides, selection is calcined under an oxygen-containing atmosphere.Example
Such as prepare combination electrode material, the combination electrode material of Mn oxide, the combination electrode of manganese Magnesium coumpoud oxide of cobalt/cobalt oxide
Material, selection is calcined under an oxygen-containing atmosphere.
When synthesis combination electrode material main component is sulfide, complex sulfide, selection is calcined under an inert atmosphere.Example
The combination electrode material of the sulfide of cobalt is such as prepared, selection is calcined under an inert atmosphere.
Wherein, oxygen-containing atmosphere refers to the oxidizing atmosphere containing oxygen, can also be oxygenous and zero with air atmosphere
The mixed atmosphere of race's gas.
Inert atmosphere refers to the gas not reacted with participation, can be zero group gas atmosphere or nitrogen atmosphere etc..
Preferably, calcining heat is 600～900 DEG C.Calcine at this temperature, protein and peptide chain in hair can be made complete
Complete to remove, hair is sintered into graphitic carbon.
Preferably, calcination time is 2～8h.The nanoneedle to be formed so can be fully set to grow up, clinkering each other is formed good
Good continuous structure.
A kind of combination electrode material, the combination electrode material is obtained by preparation method provided by the present invention.
Combination electrode material of the present invention, its main component is metal oxide or metal sulfide, while turning comprising hair
The graphitic carbon changed.
Under a preferred embodiment, the metal oxide in the combination electrode material of the present invention is in nanometer micro-pipe shape.
Under another preferred embodiment, the metal oxide party in the combination electrode material of the present invention inherits hair
Form.
The combination electrode material of the present invention has embedding lithium activity, can be embedded in lithium ion and reversibly deviate from lithium ion.
The combination electrode material of the present invention, can be used for battery, can be also used for ultracapacitor.
A kind of battery, the battery contains combination electrode material provided by the present invention.
Wherein, battery can be lithium ion battery, or inner ion communicating battery.
In lithium ion battery, combination electrode material provided by the present invention can be used as positive electrode.
The negative material of lithium ion battery, including but not limited to carbon-based material, silica-base material, tin-based material, titanium base material.
Internally in ion exchange battery, combination electrode material provided by the present invention can be used as positive electrode.
Inner ion communicating battery, abjection-insertion reaction of its positive pole based on lithium ion, negative pole is based on the second metal ion
The reaction of deposition-dissolving, containing the lithium ion for participating in positive pole abjection-insertion reaction and participate in cathode deposition-dissolving instead in electrolyte
The second metal ion answered.
The charge-discharge principle of inner ion communicating battery is：During charging, positive active material abjection lithium ion, while adjoint
Positive active material is oxidized, and ejected electron；Electronics reaches GND via external circuit, while the second metal ion is negative
Electronics is obtained on extremely to be reduced, and is deposited on negative pole.During electric discharge, the second metal being deposited on negative pole is oxidized, and loses electricity
Son is changed into the second metal ion in electrolyte；Electronics Jing external circuit reach positive pole, and positive active material receives electronics quilt
Reduction, while in Lithium-ion embeding positive active material.
Wherein, the second metal in negative pole is preferably selected from manganese, iron, copper, zinc, chromium, nickel, tin or lead；More preferably zinc.
Internally in ion exchange battery, the aqueous solution of the electrolyte preferably containing lithium ion and the second metal ion.
The miscellaneous parts such as collector, barrier film in inner ion communicating battery and battery structure, can adopt this area
Technology known to technical staff, will not be described here！
According to annual about 15～20 centimetres of the hair growth of measuring and calculating normal person, and normal person there are about 100,000 hairs；Therefore conduct
The hair of biological template of the present invention, its resource is very abundant.
At present some small tools or the ornament such as wig etc are made using mostly for hair, its technology contains
Amount and added value be not high.Using the method for the present invention, the added value of hair can be effectively improved.In addition, the present invention is for hair
The requirement sent out is low, is not limited by factors such as length, colors, can be with effectively utilizes hair wastes the like waste.Which further improves
The utilization rate and increase added value of hair.
In sum, the method for the present invention, is sustainable development to environment.The present invention its operation is simple, be not required to
Want complicated and point-device operational process of craft.The present invention need not be as collosol and gel be sent out using chemistry such as a large amount of alkoxide
Reagent, environmental protection.The combination electrode material of the present invention has special structural form, and with excellent electrochemistry
Energy.
Below in conjunction with specific embodiment, the present invention will be further elaborated and explanation.
Embodiment 1
From the hair that barber shop collects, it is cut into and is about 5cm sizes.The hair for cutting is soaked in ethanol 30 minutes,
Then again in the aqueous solution of nitric acid of 0.25mol/L soak 30 minutes.The last immersion in the NaOH aqueous solution of 0.5mol/L is lived
Change 1h.The hair of activation is filtered, and cleans up post-drying.
The hair after 5 grams of above-mentioned drying is weighed, in distributing it to ethyl acetate, dispersion is obtained.By 50ml's
Source metal solution（1mol/L Mg(NO3)2、1mol/L Mn(NO3)2）In being added to dispersion.By dispersion at room temperature
Place 2h.
Hair is filtered from dispersion, and is cleaned up, be then dried to constant weight at 110 DEG C.
By dried hair, 8h is calcined at 900 DEG C in air atmosphere.
Combination electrode material is obtained, A1 is denoted as.
Embodiment 2
From the hair that barber shop collects, it is cut into and is about 5cm sizes.The hair for cutting is soaked in ethanol 30 minutes,
Then again in the aqueous solution of nitric acid of 0.25mol/L soak 30 minutes.The last immersion in the NaOH aqueous solution of 0.5mol/L is lived
Change 1h.The hair of activation is filtered, and cleans up post-drying.
The hair after 5 grams of above-mentioned drying is weighed, in distributing it to ethyl acetate, dispersion is obtained.By 50ml's
1mol/L Mg(NO3)2Solution is added in dispersion, after place 2h at room temperature.
Hair is leached, in being distributed to equivalent ethyl acetate, the 1mol/L Mn (NO of 50ml is added3)2Solution, after in room
Temperature is lower to place 2h.
Hair is filtered, and is cleaned up, be then dried to constant weight at 110 DEG C.
By dried hair, 8h is calcined at 900 DEG C in air atmosphere.
Combination electrode material is obtained, A2 is denoted as.
Embodiment 3
From the hair that barber shop collects, it is cut into and is about 5cm sizes.The hair for cutting is soaked in ethanol 30 minutes,
Then again in the aqueous solution of nitric acid of 0.25mol/L soak 30 minutes.The last immersion in the NaOH aqueous solution of 0.5mol/L is lived
Change 1h.The hair of activation is filtered, and cleans up post-drying.
The hair after 5 grams of above-mentioned drying is weighed, in distributing it to ethyl acetate, dispersion is obtained.By 50ml's
Source metal solution（1mol/L LiNO3、1mol/L Co(NO3)2）In being added to dispersion.Dispersion is put at room temperature
Put 2h.
Hair is filtered from dispersion, and is cleaned up, be then dried to constant weight at 110 DEG C.
By dried hair, 8h is calcined at 700 DEG C in air atmosphere.
Combination electrode material is obtained, A3 is denoted as.
Embodiment 4
As different from Example 3, air atmosphere is replaced with argon gas atmosphere, other parts are with embodiment 3.
Combination electrode material is obtained, A4 is denoted as.
Embodiment 5
From the hair that barber shop collects, it is cut into and is about 5cm sizes.The hair for cutting is water-soluble in the NaOH of 0.5mol/L
Immersion activation 4h in liquid.The hair of activation is filtered, and is cleaned to the pH of cleaning solution to 8, post-drying.
The hair after 5 grams of above-mentioned drying is weighed, in distributing it to ethyl acetate, dispersion is obtained.By 50ml's
Source metal solution（1mol/L Mn(NO3)2）In being added to dispersion.Dispersion is placed at room temperature 24h.
Hair is filtered from dispersion, and is cleaned up, be then dried to constant weight at 110 DEG C.
By dried hair, 6h is calcined at 600 DEG C in air atmosphere.
Combination electrode material is obtained, A5 is denoted as.
Embodiment 6
From the hair that barber shop collects, it is cut into and is about 5cm sizes.The hair for cutting is water-soluble in the NaOH of 0.5mol/L
Immersion activation 4h in liquid.The hair of activation is filtered, and is cleaned to the pH of cleaning solution to 8, post-drying.
The hair after 5 grams of above-mentioned drying is weighed, in distributing it to ethyl acetate, dispersion is obtained.By 50ml's
Source metal solution（1mol/L Mg(NO3)2, 1mol/L Mn (NO3)2）In being added to dispersion.By dispersion at room temperature
Place 24h.
Hair is filtered from dispersion, and is cleaned up, be then dried to constant weight at 110 DEG C.
By dried hair, 6h is calcined at 600 DEG C in air atmosphere.
Combination electrode material is obtained, A6 is denoted as.
Embodiment 7
From the hair wastes that barber shop collects, the immersion activation 2h in the NaOH aqueous solution of 0.1mol/L.By the hair of activation
Filter, clean to the pH of cleaning solution to 8, post-drying.
The hair after 5 grams of above-mentioned drying is weighed, in distributing it to ethyl acetate, dispersion is obtained.By 50ml's
Source metal solution（0.004mol/L AlCl3）In being added to dispersion.Dispersion is placed at room temperature 24h.
Hair is filtered from dispersion, and is cleaned up, be then dried to constant weight at 110 DEG C.
By dried hair, 2h is calcined at 800 DEG C in air atmosphere.
Combination electrode material is obtained, A7 is denoted as.
Embodiment 8
From the hair wastes that barber shop collects, the immersion activation 2h in the NaOH aqueous solution of 0.1mol/L.By the hair of activation
Filter, clean to the pH of cleaning solution to 8, post-drying.
The hair after 5 grams of above-mentioned drying is weighed, in distributing it to ethyl acetate, dispersion is obtained.By 50ml's
Source metal solution（0.004mol/L AlCl3、0.004mol/L FeCl3）In being added to dispersion.By dispersion in room temperature
Lower placement 24h.
Hair is filtered from dispersion, and is cleaned up, be then dried to constant weight at 110 DEG C.
By dried hair, 2h is calcined at 800 DEG C in air atmosphere.
Combination electrode material is obtained, A8 is denoted as.
Embodiment 9
From the hair wastes that barber shop collects, the immersion activation 2h in the NaOH aqueous solution of 0.1mol/L.By the hair of activation
Filter, clean to the pH of cleaning solution to 8, post-drying.
The hair after 5 grams of above-mentioned drying is weighed, in distributing it to ethyl acetate, dispersion is obtained.By 50ml's
Source metal solution（0.004mol/L NiCl2）In being added to dispersion.Dispersion is placed at room temperature 24h.
Hair is filtered from dispersion, and is cleaned up, be then dried to constant weight at 110 DEG C.
By dried hair, 2h is calcined at 800 DEG C in air atmosphere.
Combination electrode material is obtained, A9 is denoted as.
Embodiment 10
From the hair wastes that barber shop collects, the immersion activation 2h in the NaOH aqueous solution of 0.1mol/L.By the hair of activation
Filter, clean to the pH of cleaning solution to 8, post-drying.
The hair after 5 grams of above-mentioned drying is weighed, in distributing it to ethyl acetate, dispersion is obtained.By 50ml's
Metal salt solution（0.004mol/L CuCl）In being added to dispersion.Dispersion is placed at room temperature 24h.
Hair is filtered from dispersion, and is cleaned up, be then dried to constant weight at 110 DEG C.
By dried hair, 2h is calcined at 800 DEG C in air atmosphere.
Combination electrode material is obtained, A10 is denoted as.
Embodiment 11
From the hair wastes that barber shop collects, the immersion activation 2h in the NaOH aqueous solution of 0.1mol/L.By the hair of activation
Filter, clean to the pH of cleaning solution to 8, post-drying.
The hair after 5 grams of above-mentioned drying is taken, in distributing it to ethyl acetate, dispersion is obtained.By the gold of 50ml
Category salting liquid（0.004mol/L FeCl3）In being added to dispersion.Dispersion is placed at room temperature 24h.
Hair is filtered from dispersion, and is cleaned up, be then dried to constant weight at 110 DEG C.
By dried hair, 2h is calcined at 800 DEG C in air atmosphere.
Combination electrode material is obtained, A11 is denoted as.
Performance test：
XRD is tested：
Powder x-ray diffraction analysis instrument：It is equipped with the Bruker D8 diffraction analysis instrument of LynxEye detectors.Wherein, X is penetrated
Line is the K alpha rays of Cu（Wavelength）, incident optical slits be 6mm, absorbent be Ni.
X-ray diffraction analysis are carried out to combination electrode material using above-mentioned powder x-ray diffraction analysis instrument.It is compound to analyze
The composition of electrode material and the crystalline structure of material.
SEM is tested：
Combination electrode material is tested using LEO FESEM1530 field emission scanning electron microscopes.To observe institute
Obtain the microscopic appearance and grain diameter of combination electrode material.
The preparation of test lithium ion battery：
By combination electrode material A1-A11, conductive agent acetylene black（Alfa Aesar companies）With binding agent Kynoar
（Arkema companies）By weight it is 80:10:10 are added to 1-METHYLPYRROLIDONE（Sigma companies）Slurry is made, then will
Positive pole is made on slurry coating graphite cake.
By LiPF6（Sigma companies）Volume ratio is dissolved in for 1:1 ethylene carbonate（EC）/ diethyl carbonate（DEC）
（Sigma companies）In, make the LiPF of 1mol/L6Nonaqueous electrolytic solution.
Positive pole and lithium piece and nonaqueous electrolytic solution are assembled into into CR2032 type batteries.
The test preparation of inner ion communicating battery：
By combination electrode material A1-A11, conductive agent acetylene black（Alfa Aesar companies）With binding agent Kynoar
（Arkema companies）It is 80 according to weight ratio:10:10 are added to 1-METHYLPYRROLIDONE（Sigma companies）Slurry is made, then
Slurry is coated and make positive pole on Copper Foil.
Lithium chloride and zinc chloride are dissolved in deionized water, electrolyte is made.
Positive pole and zinc metal sheet and electrolyte are assembled into into battery.
Fig. 1 (a)-Fig. 1 (d) is that hair is schemed in the SEM of different phase.Wherein, Fig. 1 (a) is the hair without any process
SEM figure；Fig. 1 (b) is the SEM figures of the hair after NaOH activation；Fig. 1 (c) is the SEM for soaking the hair after source metal solution
Figure；Fig. 1 (d) is the SEM figures for soaking the hair after washing after source metal solution.
Compare the hair structure that can be seen that after activation from Fig. 1 (a) and Fig. 1 (b) significantly not change, simply
Hair dimension is elongated.From Fig. 1 (c) as can be seen that adsorption of metal ions on cuticular surface, and surface formed nanometer sheet and
Nanoneedle, on the surface of hair hierarchy is produced.These nanometer sheets or nanoneedle have about the same length and diameter.From
As can be seen that after water washing, metal ion is dissolved into again water and suffers Fig. 1 (d).
Fig. 2 (a), (b) are respectively SEM figures of the combination electrode material A1 under different amplification；Fig. 3 (a), (b) are respectively
The SEM for being combination electrode material A2 under different amplification figures.
From Fig. 2 (a), (b) and Fig. 3 (a), (b) as can be seen that there is nanoparticle in the combination electrode material for synthesizing of the invention
Son.And most material is formed by nano-scale and micron size agglomeration, still can be with the offspring of aggregation
It was observed that some inherit the form of hair.
After testing, the main component of combination electrode material A1 is MgMn2O4And graphitic carbon, and the master of combination electrode material A2
Composition is wanted to be Mg2MnO4And graphitic carbon.
Fig. 4 is the XRD of electrode material A1.
Fig. 5 is that in the aqueous solution at the same time containing lithium ion and zinc ion, sweep speed is the combination electrode material under 0.5mV/s
The cyclic voltammetry curve of material A1 and A2.
From fig. 4, it can be seen that the cyclic voltammetry curve of combination electrode material A1 and A2 clearly shows:Combination electrode material
The reversible peak and irreversible peak of material A1 and A2 is respectively positioned on voltage range 0.4V to 2.1V vs Zn2+Within/Zn.
Fig. 6 (a) is the voltage curve of inner ion communicating battery made by battery material A1.
Fig. 6 (b) is the voltage curve of inner ion communicating battery made by battery material A2.
From Fig. 6 (a), (b) as can be seen that the position at above-mentioned reversible peak and irreversible peak, not with charge/discharge curve
Platform or slope correspondence.
Fig. 7 is cycle performance figure under lithium ion battery 0.1C made by combination electrode material A2.
From figure 7 it can be seen that combination electrode material A2 has very high specific capacity in lithium ion battery, its specific capacity is remote
Much larger than the LiMn of same type2O4Specific capacity（About 130mAh/g）.This shows in lithium ion battery, combination electrode material A1
Electrochemical reaction be not only embedding lithium, may also include decomposition reaction and proton intercalation reaction.
Fig. 8 is the XRD of combination electrode material A3.Wherein, the vertical line of 1 indication is standard LiCoO2Feature in collection of illustrative plates
Peak, the vertical line of 2 indications is the characteristic peak in Standard graphite carbon collection of illustrative plates, and the vertical line of 3 indications is standard Co3O4Characteristic peak in collection of illustrative plates,
The vertical line of 4 indications is the characteristic peak in standard CoO collection of illustrative plates.
From figure 8, it is seen that in combination electrode material A3 and not containing LiCoO2；Combination electrode material A3 contain CoO,
Co3O4And graphitic carbon.Calculated according to Le Bail tracing analysis, its mass percentage content is respectively 30%, 30% and 40%.
Fig. 9 is the voltage-specific capacity curve of lithium ion battery made by combination electrode material A3.
From fig. 9, it can be seen that lithium ion battery made by combination electrode material A3, is 0.2～3V in voltage（vs.Li+/
Li）, total reversible capacity is 1000mAh/g under 0.2C.
This explanation combination electrode material A3 has very excellent specific capacity.In addition to embedding lithium capacity, may also with it is compound
The non-faraday reaction of electrode material is relevant.
Figure 10 is the XRD of combination electrode material A4.Wherein, the vertical line of C indications is the feature in Standard graphite carbon collection of illustrative plates
Peak, the vertical line of S indications is standard elemental sulfur S8Characteristic peak in collection of illustrative plates.
From fig. 10 it can be seen that combination electrode material A4 contains Co9S8、S8And graphitic carbon.According to LeBail tracing analysis meters
Calculate, its mass percentage content is respectively 42%, 18% and 40%.
Figure 11 is the voltage-specific capacity curve of lithium ion battery made by combination electrode material A4.
It can be seen from fig. 11 that total discharge capacity of combination electrode material A4 nearly reaches 2000mAh/g, and in voltage
Scope 0.8V vs.Li+The specific capacity of/more than Li about 600mAh/g.This shows that combination electrode material A4 has very high specific volume
Amount.
It can also be seen that more than voltage 2.4V is not observed discharge platform from Figure 11, this explanation combination electrode material
Sulphur in A4 does not have electro-chemical activity.
Figure 12 (a), (b) scheme for the SEM of combination electrode material A5.
From Figure 12 (b) as can be seen that nano-particle has very well-crystallized structure, crystalline texture is in polygonal shape.This
A little nano-particles remain the form of a part of hair.
Figure 13 is the XRD of combination electrode material A5.Wherein, vertical line is the characteristic peak of Mn3O4.
As can be seen from Figure 13, the main component of combination electrode material A5 is the Mn of spinel structure3O4。
Figure 14 is that combination electrode material A5 makes charging and discharging curve of the lithium ion test battery under 0.5C.
As can be seen from Figure 14, the first discharge specific capacity of combination electrode material A5 is about 1005mAh/g, and this connects very much
Nearly Mn3O4Theoretical specific capacity.
Figure 15 is the cycle performance figure of combination electrode material A5.
It can be seen from fig. 15 that after 20 circulations, although the specific capacity of combination electrode material A5 decays to
380mAh/g, but this is still above the theoretical specific capacity of negative electrode material graphite.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (20)
1. a kind of preparation method of combination electrode material, it is characterised in that the preparation method includes：Hair is connect with activator
Touching activates hair；Hair after activation is dispersed in decentralized medium, source metal solution is subsequently adding and is soaked with adsorbing metal
Ion, then the hair after adsorbing metal ions is calcined under oxygen-containing atmosphere or inert atmosphere, obtain containing metal oxide or
The combination electrode material of metal sulfide.
2. preparation method according to claim 1, it is characterised in that：The hair is to soak in hair with activating agent
In activator.
3. preparation method according to claim 1, it is characterised in that：The activator is NaOH or lithium hydroxide.
4. preparation method according to claim 1, it is characterised in that：The concentration of the activator is 0.1～1mol/L.
5. preparation method according to claim 1, it is characterised in that：The time of the activation is 1～24h.
6. preparation method according to claim 1, it is characterised in that：The preparation method is additionally included in before hair activation
Prerinse step；The prerinse step includes washing hair in cleaning agent.
7. preparation method according to claim 6, it is characterised in that：The time of the washing is 15～60 minutes.
8. preparation method according to claim 6, it is characterised in that：The cleaning agent includes degreasing agent, the degreasing agent
One kind in ethanol, acetone, hexane, ethylenediamine tetra-acetic acid and dodecyl sodium sulfate.
9. preparation method according to claim 6, it is characterised in that：The cleaning agent includes foreign metal remover, institute
Foreign metal remover is stated selected from nitric acid and/or iron chloride.
10. preparation method according to claim 9, it is characterised in that：The mass percentage concentration of the nitric acid be 0.5～
2%。
11. preparation methods according to claim 1, it is characterised in that：The decentralized medium is ethyl acetate.
12. preparation methods according to claim 1, it is characterised in that：Metal ion in the source metal solution is selected from
One or more in magnesium ion, copper ion, manganese ion, cobalt ions, nickel ion, iron ion and aluminium ion.
13. preparation methods according to claim 1, it is characterised in that：Anion in the source metal solution is selected from sulphur
One or more in acid ion, nitrate ion, acetate ion and acetoacetate radical ion.
14. preparation methods according to claim 1, it is characterised in that：In adsorbing metal ions, the number of times of the immersion
For at least twice；And it is adjacent twice soak between, hair is leached from source metal solution.
15. preparation methods according to claim 1, it is characterised in that：In adsorbing metal ions, the time of immersion is 2
～24h.
16. preparation methods according to claim 1, it is characterised in that：In adsorbing metal ions, the pH of the solution of immersion
It is worth for 8～9.
17. preparation methods according to claim 1, it is characterised in that：The temperature of the calcining is 600～900 DEG C.
18. preparation methods according to claim 1, it is characterised in that：The time of the calcining is 2～8h.
A kind of 19. combination electrode materials, it is characterised in that：The system that the combination electrode material passes through one of claim 1～18
Preparation Method is obtained.
A kind of 20. batteries, it is characterised in that：The battery contains the combination electrode material described in claim 19.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410072989.7A CN104425803B (en) | 2013-08-30 | 2014-02-28 | Method for preparing composite electrode material, composite electrode material and battery |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310388351 | 2013-08-30 | ||
| CN201310388351X | 2013-08-30 | ||
| CN201410072989.7A CN104425803B (en) | 2013-08-30 | 2014-02-28 | Method for preparing composite electrode material, composite electrode material and battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104425803A CN104425803A (en) | 2015-03-18 |
| CN104425803B true CN104425803B (en) | 2017-04-12 |
Family
ID=52974194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410072989.7A Active CN104425803B (en) | 2013-08-30 | 2014-02-28 | Method for preparing composite electrode material, composite electrode material and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104425803B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355852A (en) * | 2015-11-16 | 2016-02-24 | 四川大学 | Carbon/metal oxide core-shell-type three dimensional nanometer fiber bundle and preparation method thereof |
| CN105932283A (en) * | 2016-06-30 | 2016-09-07 | 谢振华 | Lithium ion battery and negative electrode material thereof and preparation method of negative electrode material |
| CN106390971B (en) * | 2016-11-30 | 2018-11-30 | 内蒙古大学 | A kind of production method of charcoal based titanium dioxide catalysis material |
| CN109758142A (en) * | 2019-01-31 | 2019-05-17 | 青岛光电医疗科技有限公司 | A kind of electrode based on acquiring biological electric signals |
| CN111675285B (en) * | 2020-05-21 | 2021-04-27 | 天津大学 | Method for manufacturing three-dimensional ordered pore electric desalting electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102394294A (en) * | 2011-11-29 | 2012-03-28 | 上海交通大学 | Preparation method of highly graphitized activated carbon-transition metal oxide nanocomposite material |
| CN102602931A (en) * | 2012-03-27 | 2012-07-25 | 武汉纺织大学 | Method for preparing medical active carbon tube by utilizing hairs |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090098033A1 (en) * | 2006-02-10 | 2009-04-16 | Kun Lian | Carbon-Encased Metal Nanoparticles and Sponges, Methods of Synthesis, and Methods of Use |
-
2014
- 2014-02-28 CN CN201410072989.7A patent/CN104425803B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102394294A (en) * | 2011-11-29 | 2012-03-28 | 上海交通大学 | Preparation method of highly graphitized activated carbon-transition metal oxide nanocomposite material |
| CN102602931A (en) * | 2012-03-27 | 2012-07-25 | 武汉纺织大学 | Method for preparing medical active carbon tube by utilizing hairs |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104425803A (en) | 2015-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1171335C (en) | Positive active material for lithium secondary cell and its preparing method | |
| Ortiz et al. | A novel architectured negative electrode based on titania nanotube and iron oxide nanowire composites for Li-ion microbatteries | |
| CN103178258B (en) | Alumina-coated is modified the preparation method of lithium nickel cobalt manganese oxygen positive electrode | |
| CN106099050B (en) | Active material compound particle, electrode active material layer and all-solid lithium battery | |
| CN103460456B (en) | Positive active material particle powder and manufacture method thereof and rechargeable nonaqueous electrolytic battery | |
| CN104425803B (en) | Method for preparing composite electrode material, composite electrode material and battery | |
| CN104956527B (en) | Transition metal hexacyanoferrate battery cathode, transition metal hexacyanoferrate cathode battery, method for synthesizing a transition metal hexacyanoferrate battery material, method for fabricating a transition metal hexacyanoferrate battery cathode electrode, and method for using a transition metal hexacyanoferrate battery | |
| CN103926265B (en) | A kind of in-situ synchronization observation and the method for analyzing lithium ion cell electrode reaction | |
| Meng et al. | Spent alkaline battery-derived manganese oxides as efficient oxygen electrocatalysts for Zn–air batteries | |
| CN110048084A (en) | All-solid-state battery cathode mix, all-solid-state battery anode, all-solid-state battery and their manufacturing method | |
| CN108767216A (en) | Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope | |
| CN108461739A (en) | A kind of high performance lithium ionic cell cathode material Fe7S8The preparation method of/C | |
| CN103956483A (en) | Preparation method and application of zinc cobaltate/nickel oxide core-shell nanowire array | |
| Xing et al. | Novel recycling approach to regenerate a LiNi0. 6Co0. 2Mn0. 2O2 cathode material from spent lithium-ion batteries | |
| CN109565048A (en) | The manufacturing method of positive active material for non-aqueous electrolyte secondary battery, the positive active material for non-aqueous electrolyte secondary battery | |
| CN106711440A (en) | Nano flaky sodium-ion battery anode material and preparation method thereof | |
| CN108615612A (en) | A kind of flower-shaped cobaltosic oxide-graphene composite material and preparation method thereof | |
| Lee et al. | The electrochemical capacities and cycle retention of electrochemically deposited Cu2O thin film toward lithium | |
| CN108432001A (en) | Manufacturing method, positive active material, anode and the lithium rechargeable battery of positive active material | |
| CN106252594B (en) | A kind of ball-shaped lithium-ion battery anode material and its synthetic method with nanoscale two-phase coexistent structure | |
| JPH07101728A (en) | Lithium manganese double oxide, its production and application | |
| CN107381656A (en) | A kind of preparation method of lithium ion battery negative material | |
| CN112624198A (en) | Method for synthesizing high-activity layered zinc ion secondary battery anode material by one-step method at room temperature | |
| CN104737338A (en) | A new solid solution composite LiMVO4-liNi1-x-yCoxMnyO2 material for rechargeable lithium ion batteries | |
| WO2014115973A1 (en) | Fluorine compound-coated cathode active material for lithium secondary battery and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |