CN107958992A - Porous binary NiMn oxide lithium cell negative pole materials and preparation method thereof - Google Patents
Porous binary NiMn oxide lithium cell negative pole materials and preparation method thereof Download PDFInfo
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- CN107958992A CN107958992A CN201711099525.5A CN201711099525A CN107958992A CN 107958992 A CN107958992 A CN 107958992A CN 201711099525 A CN201711099525 A CN 201711099525A CN 107958992 A CN107958992 A CN 107958992A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/0438—Processes of manufacture in general by electrochemical processing
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a kind of porous binary NiMn oxide lithium cell negative pole materials and preparation method thereof, which includes the following steps：Using the NiMn alloys that Mn percentage by weights are 50 80% as raw material, NiMn alloy sheets are prepared；Removal alloying processing is carried out to NiMn alloy sheets, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, the porous NiMn alloy sheets after being heat-treated；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, to obtain porous binary NiMn oxide lithium cell negative pole materials, wherein autoxidation processing is heat-treatment oxidation or activation polarization oxidation processes in atmosphere.The present invention preparation method is simple, cost is low, and due to being directly to form oxide on NiMn alloy substrates, so oxide and matrix are tightly combined.Property indices by porous binary NiMn oxide lithium cell negative pole materials made from the preparation method of the present invention are all very excellent.
Description
Technical field
The present invention relates to a kind of lithium cell negative pole material and preparation method thereof, more particularly to a kind of porous binary NiMn oxides
Lithium cell negative pole material and preparation method thereof.
Background technology
Lithium ion battery is used widely as a kind of efficiently chargeable energy storage device in daily life production.Lithium from
Sub- battery is mainly made of four part such as positive and negative pole material, membrane, electrolyte, and the quality of wherein positive and negative pole material performance is serious
It has impact on its performance.Negative material with relatively low current potential because can improve lithium ion battery applications voltage range.Lithium cell negative pole
Material mainly includes commercialization activated carbon, tinbase, silicon substrate and transition group metallic oxide etc..Wherein transition group metallic oxide
Because paid much attention to high theoretical specific capacity be subject to this area.But because transition group metallic oxide poorly conductive,
In charge and discharge process the shortcomings that easy expansion and dusting, therefore its application is restricted.To improve the conduction of transition group metallic oxide
Property and improve service life cycle, many researchs are directed to introducing conductive additive or conductive reinforcement to solve these defects.
The method that the transition group metallic oxide powder of different-shape and conductive agent, binding agent are carried out by batch mixing film by conventional method
Highly practical film cathode material can be prepared.But because the addition of conductive agent and binding agent, cause preparation method complicated
It is unfavorable for quickly preparing lithium cell negative pole, and the lithium cell negative pole poor circulation being prepared, and improve production cost.It is logical
Cross the conductive reinforcement of introducing, the high conductivity of reinforcement, the advantage of high-specific surface area can be efficiently used, thus prepare it is new from
Combination electrode is supported, such electrode has preferable performance.But lead to during compound lithium cell negative pole material is prepared
Frequently with physical deposition methods, chemistry, electrochemical deposition method and hydro-thermal reaction etc. either physically or chemically, its active material is with leading
It is difficult to combine closely between electric reinforcement.In long-time cyclic process, active material, which comes off, can seriously affect negative material performance
And limit commercial applications.
To solve the problems, such as above-mentioned transition group metallic oxide poorly conductive existing for lithium electricity industry at present, using current pole
The removal alloying of tool advantage-polarization oxidizing process, successfully prepares the self-supporting electrode material of the oxide of surface self-grown, it is lived
Property material and conductive porous metallic matrix there is the relation of Lattice Matching, so both can compact growth together, it is difficult to de-
Fall.It is advantageous that：1st, the oxide that binary system is formed forms collaboration system and has the function that to suppress volumetric expansion mutually；2、
Porous metals can effectively improve interface binding power by autoxidizable method and improve conductive capability, be beneficial to as conducting base
The transmission of electronics, ion；3rd, high specific surface area can load more active materials, so as to improve specific capacity；4th, magnesium-yttrium-transition metal
Oxide rich in mineral resources, and it is simple for electrode method using made of metal, cost is lower.
The information for being disclosed in the background section is merely intended to understanding of the increase to the general background of the present invention, without answering
It has been the prior art well known to persons skilled in the art when being considered as recognizing or implying the information structure in any form.
The content of the invention
It is an object of the invention to provide a kind of preparation method of porous binary NiMn oxide lithium cell negative pole materials, so that
The shortcomings that overcoming the prior art.
To achieve the above object, the present invention provides a kind of preparation side of porous binary NiMn oxide lithium cell negative pole materials
Method, it is characterised in that：Method includes the following steps：NiMn alloys using Mn percentage by weights as 50-80% are raw material, are prepared
NiMn alloy sheets；Removal alloying processing is carried out to NiMn alloy sheets, to obtain porous NiMn alloy sheets；To porous NiMn alloy sheets
It is heat-treated, wherein process of thermal treatment is：Taken the photograph using hydrogen as reduction and protective atmosphere, heat treatment temperature for 400-1000
Family name's degree, the time of heat treatment is 10min-180min, the porous NiMn alloy sheets after being heat-treated；After heat treatment
Porous NiMn alloy sheets carry out surface autoxidation processing, to obtain porous binary NiMn oxide lithium cell negative pole materials, autoxidation
Processing is heat-treatment oxidation or activation polarization oxidation processes in atmosphere.
Preferably, in above-mentioned technical proposal, wherein, preparing NiMn alloy sheets is specially：Prepared using melt-spun method thick
Spend the NiMn alloy sheets of 20-50um or obtain single phase solid solution NiMn alloy pigs using melting and casting legal system, then rolled, obtained
To the NiMn alloy sheets that thickness is 20-500um.
Preferably, in above-mentioned technical proposal, removal alloying processing is chemical removal alloying method, and chemical removal alloying method is specific
Step is：With the one or more in ammonium sulfate, dilute hydrochloric acid or dilute sulfuric acid for corrosive liquid, in the bar that temperature is 20-80 degrees Celsius
NiMn alloy sheets are corroded under part, the corrosion treatment time is 30-300 minutes.
Preferably, in above-mentioned technical proposal, removal alloying processing is electrochemistry removal alloying method, electrochemistry removal alloying method
Comprise the concrete steps that：Using ammonium sulfate as corrosive liquid, NiMn alloy sheets are carried out under conditions of -0.4-0.9V in corrosion potential rotten
Erosion, corrosion treatment time are 30-1200 minutes.
Preferably, in above-mentioned technical proposal, heat-treatment oxidation is specifically in atmosphere：Hot place is carried out in air atmosphere
Reason, the temperature range of heat treatment is 100-400 degrees Celsius, and the time of heat treatment is 10-120min.
Preferably, in above-mentioned technical proposal, activation polarization oxidation processes are specifically：Potassium hydroxide, sodium hydroxide or
In lithium hydroxide solution to after heat treatment porous NiMn alloy sheets carry out polarization process, solution concentration 0.5-6mol/L,
Polarizing voltage is less than 1V, polarization time 10-600s, and gas is protected in argon gas, nitrogen etc. to the porous metals after obtained polarization
It is heat-treated under atmosphere, obtains the NiMn oxide lithium cell negative pole materials of surface only supported active oxide.
Preferably, in above-mentioned technical proposal, the temperature of heat treatment is 300-900 degrees Celsius.
Another object of the present invention is to provide a kind of porous binary NiMn oxide lithium cell negative pole materials, the lithium cell negative pole
Material is prepared by aforementioned preparation process.
Compared with prior art, the present invention has the advantages that：1st, the present invention is by directly preparing NiMn alloy-baseds
Body, then directly carries out removal alloying processing to NiMn alloy substrates, so as to directly obtain porous NiMn alloys；2nd, in protection gas
Heat treatment in atmosphere, and the control to heat treatment process is combined, so as to control the pore size and pore size distribution of NiMn micropores；3rd, exist
On this basis, by last oxidation processes, directly obtain using micropore NiMn alloys as matrix, be evenly distributed with collective
The lithium cell negative pole material of oxide skin(coating).Existing preparation method is simple than in the prior art for the method that the present invention uses, and cost is more
It is low, and due to being directly to form oxide on NiMn alloy substrates, so the combination of oxide and matrix is closer.
Brief description of the drawings
Fig. 1 is the schematical three-dimensional flow chart of the preparation process of the present invention.
Embodiment
Below in conjunction with the accompanying drawings, the embodiment of the present invention is described in detail, it is to be understood that the guarantor of the present invention
Protect scope and from the limitation of embodiment.
Explicitly indicated that unless otherwise other, otherwise in entire disclosure and claims, term " comprising " or its change
Change such as "comprising" or " including " etc. and will be understood to comprise stated element or part, and do not exclude other members
Part or other parts.
In the present invention, alloy and various solvents, solution are all available from general chemical shop.Electrochemical treatments can use
The electrochemical workstation of various models, brand, the selection of electrochemical workstation in itself do not have materially affect for the present invention.At heat
Reason stove is the heat-treatment furnace of any kind well known in the art.Battery testing is carried out using cell tester well known in the art.
Fig. 1 is the schematical three-dimensional flow chart of the preparation process of the present invention.
Embodiment 1
The NiMn alloys for being 50% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 1000 degrees Celsius, and the time of heat treatment is 10min, obtains heat
Porous NiMn alloy sheets after processing；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from oxygen
Change processing is heat-treatment oxidation in atmosphere, wherein, the NiMn alloy sheets of thickness 20um are prepared using melt-spun method, utilize change
Removal alloying method is learned, using ammonium sulfate as corrosive liquid, NiMn alloy sheets are corroded under conditions of being 20 degrees Celsius in temperature, it is rotten
It is 300 minutes to lose processing time, is heat-treated in air atmosphere, and the temperature range of heat treatment is 400 degrees Celsius, heat treatment
Time be 10min.Finally obtain porous binary NiMn oxide lithium cell negative pole materials.
Embodiment 2
The NiMn alloys for being 80% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 400 degrees Celsius, and the time of heat treatment is 180min, obtains heat
Porous NiMn alloy sheets after processing；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from oxygen
Change processing is heat-treatment oxidation in atmosphere, wherein, the NiMn alloy sheets of thickness 50um are prepared using melt-spun method, utilize change
Removal alloying method is learned, using ammonium sulfate as corrosive liquid, NiMn alloy sheets are corroded under conditions of being 80 degrees Celsius in temperature, it is rotten
It is 30 minutes to lose processing time, is heat-treated in air atmosphere, and the temperature range of heat treatment is 100 degrees Celsius, heat treatment
Time be 120min.Finally obtain porous binary NiMn oxide lithium cell negative pole materials.
Embodiment 3
The NiMn alloys for being 80% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 300 degrees Celsius, and the time of heat treatment is 180min, obtains heat
Porous NiMn alloy sheets after processing；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from oxygen
Change processing is heat-treatment oxidation in atmosphere, wherein, single phase solid solution NiMn alloy pigs are obtained using melting and casting legal system, with laggard
Row rolling, obtains the NiMn alloy sheets that thickness is 20um, using chemical removal alloying method, using dilute hydrochloric acid as corrosive liquid, in temperature
To corrode to NiMn alloy sheets under conditions of 80 degrees Celsius, the corrosion treatment time is 30 minutes, is carried out in air atmosphere
Heat treatment, the temperature range of heat treatment is 100 degrees Celsius, and the time of heat treatment is 120min.Finally obtain porous binary NiMn
Oxide lithium cell negative pole material.
Embodiment 4
The NiMn alloys for being 80% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 400 degrees Celsius, and the time of heat treatment is 180min, obtains heat
Porous NiMn alloy sheets after processing；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from oxygen
Change processing is heat-treatment oxidation in atmosphere, wherein, single phase solid solution NiMn alloy pigs are obtained using melting and casting legal system, with laggard
Row rolling, obtains the NiMn alloy sheets that thickness is 500um, using chemical removal alloying method, using dilute sulfuric acid as corrosive liquid, in temperature
To corrode to NiMn alloy sheets under conditions of 80 degrees Celsius, the corrosion treatment time is 30 minutes, is carried out in air atmosphere
Heat treatment, the temperature range of heat treatment is 100 degrees Celsius, and the time of heat treatment is 120min.Finally obtain porous binary NiMn
Oxide lithium cell negative pole material.
Embodiment 5
The NiMn alloys for being 70% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 800 degrees Celsius, and the time of heat treatment is 100min, obtains heat
Porous NiMn alloy sheets after processing；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from oxygen
Change processing is heat-treatment oxidation in atmosphere, wherein, single phase solid solution NiMn alloy pigs are obtained using melting and casting legal system, with laggard
Row rolling, obtains the NiMn alloy sheets that thickness is 30um, using chemical removal alloying method, using ammonium sulfate as corrosive liquid, in temperature
To corrode to NiMn alloy sheets under conditions of 50 degrees Celsius, the corrosion treatment time is 150 minutes, is carried out in air atmosphere
Heat treatment, the temperature range of heat treatment is 250 degrees Celsius, and the time of heat treatment is 60min.Finally obtain porous binary NiMn oxygen
Compound lithium cell negative pole material.
Embodiment 6
The NiMn alloys for being 70% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 900 degrees Celsius, and the time of heat treatment is 100min, obtains heat
Porous NiMn alloy sheets after processing；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from oxygen
Change processing is activation polarization oxidation processes, wherein, single phase solid solution NiMn alloy pigs are obtained using melting and casting legal system, with laggard
Row rolling, obtains the NiMn alloy sheets that thickness is 30um, using electrochemistry removal alloying method, electrochemistry removal alloying method specifically walks
Suddenly it is：Using ammonium sulfate as corrosive liquid, NiMn alloy sheets are corroded under conditions of 0.9V in corrosion potential, during corrosion treatment
Between be 30 minutes, activation polarization oxidation processes are specifically：In potassium hydroxide, sodium hydroxide or lithium hydroxide solution to heat at
Porous NiMn alloy sheets after reason carry out polarization process, solution concentration 0.5mol/L, polarizing voltage 0.9V, and the polarization time is
600s, the porous metals after obtained polarization are heat-treated under the protective atmospheres such as argon gas, nitrogen, surface is obtained and only loads
The NiMn lithium cell negative pole materials of activating oxide.
Embodiment 7
The NiMn alloys for being 70% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 800 degrees Celsius, and the time of heat treatment is 100min, obtains heat
Porous NiMn alloy sheets after processing；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from oxygen
Change processing is activation polarization oxidation processes, wherein, single phase solid solution NiMn alloy pigs are obtained using melting and casting legal system, with laggard
Row rolling, obtains the NiMn alloy sheets that thickness is 30um, using electrochemistry removal alloying method, electrochemistry removal alloying method specifically walks
Suddenly it is：Using ammonium sulfate as corrosive liquid, NiMn alloy sheets are corroded under conditions of -0.4V in corrosion potential, corrosion treatment
Time is 1200 minutes, and activation polarization oxidation processes are specifically：It is right in potassium hydroxide, sodium hydroxide or lithium hydroxide solution
Porous NiMn alloy sheets after heat treatment carry out polarization process, solution concentration 6mol/L, polarizing voltage 1V, and the polarization time is
10s, the porous metals after obtained polarization are heat-treated under the protective atmospheres such as argon gas, nitrogen, surface is obtained and only loads
The NiMn lithium cell negative pole materials of activating oxide.
Embodiment 8
The NiMn alloys for being 70% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 800 degrees Celsius, and the time of heat treatment is 100min, obtains heat
Porous NiMn alloy sheets after processing；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from oxygen
Change processing is activation polarization oxidation processes, wherein, single phase solid solution NiMn alloy pigs are obtained using melting and casting legal system, with laggard
Row rolling, obtains the NiMn alloy sheets that thickness is 30um, using electrochemistry removal alloying method, electrochemistry removal alloying method specifically walks
Suddenly it is：Using ammonium sulfate as corrosive liquid, NiMn alloy sheets are corroded under conditions of 0.6V in corrosion potential, during corrosion treatment
Between be 100 minutes, activation polarization oxidation processes are specifically：To heat in potassium hydroxide, sodium hydroxide or lithium hydroxide solution
Porous NiMn alloy sheets after processing carry out polarization process, solution concentration 3.5mol/L, polarizing voltage 0.5V, polarization time
For 300s, the porous metals after obtained polarization are heat-treated under the protective atmospheres such as argon gas, nitrogen, it is only negative to obtain surface
Carry the NiMn lithium cell negative pole materials of activating oxide.
Comparative example 1
The NiMn alloys for being 70% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 1200 degrees Celsius, and the time of heat treatment is 300min, is obtained
Porous NiMn alloy sheets after heat treatment；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from
Oxidation processes are heat-treatment oxidations in atmosphere, wherein, single phase solid solution NiMn alloy pigs are obtained using melting and casting legal system, then
Rolled, the NiMn alloy sheets that thickness is 30um are obtained, using chemical removal alloying method, using ammonium sulfate as corrosive liquid, in temperature
Spend to corrode to NiMn alloy sheets under conditions of 50 degrees Celsius, the corrosion treatment time is 150 minutes, in air atmosphere into
Row heat treatment, the temperature range of heat treatment is 250 degrees Celsius, and the time of heat treatment is 60min.Obtain surface only supported active oxygen
The lithium cell negative pole material of the NiMn of compound.
Comparative example 2
The NiMn alloys for being 70% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 800 degrees Celsius, and the time of heat treatment is 100min, obtains heat
Porous NiMn alloy sheets after processing；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from oxygen
Change processing is heat-treatment oxidation in atmosphere, wherein, single phase solid solution NiMn alloy pigs are obtained using melting and casting legal system, with laggard
Row rolling, obtains the NiMn alloy sheets that thickness is 30um, using chemical removal alloying method, using ammonium sulfate as corrosive liquid, in temperature
To corrode to NiMn alloy sheets under conditions of 120 degrees Celsius, the corrosion treatment time is 500 minutes, in air atmosphere into
Row heat treatment, the temperature range of heat treatment is 500 degrees Celsius, and the time of heat treatment is 500min.Obtain surface only supported active
The lithium cell negative pole material of the NiMn of oxide.
Comparative example 3
The NiMn alloys for being 70% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 800 degrees Celsius, and the time of heat treatment is 100min, obtains heat
Porous NiMn alloy sheets after processing；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from oxygen
Change processing is activation polarization oxidation processes, wherein, single phase solid solution NiMn alloy pigs are obtained using melting and casting legal system, with laggard
Row rolling, obtains the NiMn alloy sheets that thickness is 30um, using electrochemistry removal alloying method, electrochemistry removal alloying method specifically walks
Suddenly it is：Using ammonium sulfate as corrosive liquid, NiMn alloy sheets are corroded under conditions of -0.7V in corrosion potential, corrosion treatment
Time is 100 minutes, and activation polarization oxidation processes are specifically：It is right in potassium hydroxide, sodium hydroxide or lithium hydroxide solution
Porous NiMn alloy sheets after heat treatment carry out polarization process, solution concentration 3.5mol/L, polarizing voltage 0.9V, during polarization
Between be 800s, the porous metals after obtained polarization are heat-treated under the protective atmospheres such as argon gas, nitrogen, obtain surface only
The lithium cell negative pole material of the NiMn of supported active oxide.
Comparative example 4
The NiMn alloys for being 70% using Mn percentage by weights prepare NiMn alloy sheets as raw material；NiMn alloy sheets are carried out
Removal alloying processing, to obtain porous NiMn alloy sheets；Porous NiMn alloy sheets are heat-treated, wherein process of thermal treatment
It is：Using hydrogen as reduction and protective atmosphere, heat treatment temperature is 800 degrees Celsius, and the time of heat treatment is 100min, obtains heat
Porous NiMn alloy sheets after processing；Surface autoxidation processing is carried out to the porous NiMn alloy sheets after heat treatment, from oxygen
Change processing is activation polarization oxidation processes, wherein, single phase solid solution NiMn alloy pigs are obtained using melting and casting legal system, with laggard
Row rolling, obtains the NiMn alloy sheets that thickness is 30um, using electrochemistry removal alloying method, electrochemistry removal alloying method specifically walks
Suddenly it is：Using ammonium sulfate as corrosive liquid, NiMn alloy sheets are corroded under conditions of -0.5V in corrosion potential, corrosion treatment
Time is 500 minutes, and activation polarization oxidation processes are specifically：It is right in potassium hydroxide, sodium hydroxide or lithium hydroxide solution
Porous NiMn alloy sheets after heat treatment carry out polarization process, solution concentration 3.5mol/L, polarizing voltage 0.5V, during polarization
Between be 300s, the porous metals after obtained polarization are heat-treated under the protective atmospheres such as argon gas, nitrogen, obtain surface only
The lithium cell negative pole material of the NiMn of supported active oxide.
By the above-mentioned material prepared according to the described preparation methods of embodiment 1-8 and comparative example 1-4 according to this area
Known method prepares battery and is tested, and wherein test method is the known method that this area has.First circle in the present invention
Specific discharge capacity refers to：It is powered first under the conditions of current density is 50mA/g, the specific discharge capacity then tested；
Specific discharge capacity refers to after stabilization：After at least 1min that is powered, the specific discharge capacity of test；Specific discharge capacity multiplying power refers to：
When current density brings up to 500mA/g from 50mA/g, the change rate of specific discharge capacity；Cycle performance refers to：In current density
Tested to carry out 100 circle cycle performances under the conditions of 100mA/g, then the capacity retention ratio of battery.Test knot to above-mentioned battery
Fruit is listed in table 1.
Table 1
, can by the result of table 1, it is apparent that the method for the present invention is by reasonable step design and parameter designing
Obtain all very excellent battery of property indices.It can be seen from table in comparative example 1, due to first for adjusting
The heat treatment process of hole size is poor, so cause metallic matrix mesoporous excessive, and pore-size distribution is uneven, so have impact on
Follow-up process, the oxide-film that specifically result in follow-up autoxidation processing is uneven, with reference to force difference, so properties
It is poor.In comparative example 2,3, since the technique of autoxidation step deviates particular design, cause oxidation Rotating fields uneven, with reference to
Force difference, so properties are poor.
It is foregoing to the present invention specific exemplary embodiment description be in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explain that the certain principles of the present invention and its reality should
With so that those skilled in the art can realize and utilize the present invention a variety of exemplaries and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (8)
1. a kind of preparation method of porous binary NiMn oxide lithium cell negative pole materials, it is characterised in that the described method includes such as
Lower step：
NiMn alloys using Mn percentage by weights as 50-80% are raw material, prepare NiMn alloy sheets；
Removal alloying processing is carried out to the NiMn alloy sheets, to obtain porous NiMn alloy sheets；
Porous NiMn alloy sheets are heat-treated, wherein the process of thermal treatment is：Reduction and protection gas are used as using hydrogen
Atmosphere, heat treatment temperature are 400-1000 degrees Celsius, and the time of the heat treatment is 10min-180min, after being heat-treated
Porous NiMn alloy sheets；
Surface autoxidation processing is carried out to the porous NiMn alloy sheets after the heat treatment, to obtain the porous binary NiMn
Oxide lithium cell negative pole material, autoxidation processing are heat-treatment oxidation or activation polarization oxidation processes in atmosphere.
2. preparation method as claimed in claim 1, it is characterised in that wherein, the preparation NiMn alloy sheets are specially：Utilize
Melt-spun method prepares the NiMn alloy sheets of thickness 20-50um or obtains single phase solid solution NiMn alloys using melting and casting legal system
Ingot, is then rolled, and obtains the NiMn alloy sheets that thickness is 20-500um.
3. preparation method as claimed in claim 1, it is characterised in that the removal alloying processing is chemical removal alloying method,
The chemistry removal alloying method comprises the concrete steps that：With the one or more in ammonium sulfate, dilute hydrochloric acid or dilute sulfuric acid for corrosive liquid,
Temperature corrodes the NiMn alloy sheets under conditions of being 20-80 degrees Celsius, and the corrosion treatment time is 30-300 minutes.
4. preparation method as claimed in claim 1, it is characterised in that the removal alloying processing is electrochemistry removal alloying
Method, the electrochemistry removal alloying method comprise the concrete steps that：Using ammonium sulfate as corrosive liquid, corrosion potential -0.4-0.9V bar
The NiMn alloy sheets are corroded under part, the corrosion treatment time is 30-1200 minutes.
5. preparation method as claimed in claim 1, it is characterised in that the heat-treatment oxidation in atmosphere is specifically：Big
It is heat-treated in gas atmosphere, the temperature range of the heat treatment is 100-400 degrees Celsius, and the time of the heat treatment is 10-
120min。
6. preparation method as claimed in claim 1, it is characterised in that the activation polarization oxidation processes are specifically：In hydrogen
Polarization process is carried out to the porous NiMn alloy sheets after the heat treatment in potassium oxide, sodium hydroxide or lithium hydroxide solution,
The solution concentration is 0.5-6mol/L, and polarizing voltage is less than 1V, polarization time 10-600s, to more after obtained polarization
Mesoporous metal is heat-treated under the protective atmospheres such as argon gas, nitrogen, obtains the NiMn oxides of surface only supported active oxide
Lithium cell negative pole material.
7. preparation method as claimed in claim 1, it is characterised in that the temperature of the heat treatment is 300-900 degrees Celsius.
8. a kind of porous binary NiMn oxide lithium cell negative pole materials, it is characterised in that the lithium cell negative pole material is by such as
What the method described in one of claim 1-7 was prepared.
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| CN108735518A (en) * | 2018-05-31 | 2018-11-02 | 济南大学 | A kind of hexagonal flake manganese oxide@nickel oxide composite materials and preparation method thereof |
| CN108807890A (en) * | 2018-05-24 | 2018-11-13 | 天津工业大学 | A kind of ternary nano porous nickel vanadium manganese oxide electrode material and preparation method thereof |
| CN111009644A (en) * | 2019-11-13 | 2020-04-14 | 天津工业大学 | Preparation method of nano-porous copper surface modified MnO/graphene composite electrode |
| CN114023928A (en) * | 2021-08-31 | 2022-02-08 | 天津大学 | Preparation method for in-situ construction of bimetallic oxide integrated electrode by hierarchical porous copper |
| CN114604899A (en) * | 2022-04-11 | 2022-06-10 | 安徽工业大学 | Lithium ion battery anode material precursor and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108807890A (en) * | 2018-05-24 | 2018-11-13 | 天津工业大学 | A kind of ternary nano porous nickel vanadium manganese oxide electrode material and preparation method thereof |
| CN108735518A (en) * | 2018-05-31 | 2018-11-02 | 济南大学 | A kind of hexagonal flake manganese oxide@nickel oxide composite materials and preparation method thereof |
| CN108735518B (en) * | 2018-05-31 | 2020-07-07 | 济南大学 | Hexagonal flaky manganese oxide @ nickel oxide composite material and preparation method thereof |
| CN111009644A (en) * | 2019-11-13 | 2020-04-14 | 天津工业大学 | Preparation method of nano-porous copper surface modified MnO/graphene composite electrode |
| CN111009644B (en) * | 2019-11-13 | 2023-09-22 | 天津工业大学 | Preparation method of nano-porous copper surface modified MnO/graphene composite electrode |
| CN114023928A (en) * | 2021-08-31 | 2022-02-08 | 天津大学 | Preparation method for in-situ construction of bimetallic oxide integrated electrode by hierarchical porous copper |
| CN114604899A (en) * | 2022-04-11 | 2022-06-10 | 安徽工业大学 | Lithium ion battery anode material precursor and preparation method thereof |
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