CN106935842A - Electroplate plating solution, lithium selenium cell positive electrode and the lithium selenium cell of selenium - Google Patents
Electroplate plating solution, lithium selenium cell positive electrode and the lithium selenium cell of selenium Download PDFInfo
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- CN106935842A CN106935842A CN201710133874.8A CN201710133874A CN106935842A CN 106935842 A CN106935842 A CN 106935842A CN 201710133874 A CN201710133874 A CN 201710133874A CN 106935842 A CN106935842 A CN 106935842A
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- lithium
- positive electrode
- selenite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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- 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
Abstract
The invention provides a kind of preparation method of lithium selenium cell positive electrode, comprise the following steps：A) selenous acid or selenite, electrolytic salt, pH adjusting agent, pH buffer, surfactant and water are mixed, mixed liquor is obtained；B) mixed liquor is electroplated under 15~60 DEG C of temperature conditionss in substrate, lithium selenium cell positive electrode is obtained.The present invention uses specific electroplate liquid, coordinates specific electroplating parameter, prepares the plating selenium layer that purity is high and crystallite dimension is small, and the material that the method is prepared is used directly for lithium selenium cell, without adding any conductive agent and binding agent.The load capacity of selenium can well be controlled by controlling electroplating time, plating current potential and surface current simultaneously.The lithium selenium cell positive electrode that the preparation method of the lithium selenium cell positive electrode that the present invention is provided is prepared has excellent charging and discharging capacity and cycle performance.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly, to a kind of plating solution, lithium selenium cell positive pole for electroplating selenium
Material and lithium selenium cell.
Background technology
With the development of social economy, the sharp increase of Global Auto recoverable amount so that substantial amounts of fossil fuel is constantly consumed, by
The immense pressure problem that this global energy crisis for causing and environment face becomes increasingly conspicuous, and Development of Novel cleaning is reproducible secondary
The energy is extremely urgent.
Lithium ion battery can carry digital product, wearable as a kind of chargeable secondary energy storage system at present
The fields such as electronic device, pure electric automobile and energy-accumulating power station develop application, and people rapidly for the need of lithium ion battery
Ask more and more, performance requirement more and more higher.
In all of rechargeable secondary lithium ion battery, lithium selenium cell is with traditional by graphite and embedding lithium transition-metal oxygen
The lithium rechargeable battery of compound composition is compared to high theoretical specific capacity (675mAhg-1).Simultaneously with similar lithium sulphur
Battery is compared, although Theoretical Mass specific capacity is not good enough compared with lithium-sulfur cell.But lithium selenium cell possesses considerable volume specific volume
Amount, this has far-reaching application value in production practices.At the same time, because elemental selenium has high electronics compared to sulphur
Electric conductivity so that lithium selenium cell possesses active material utilization and more preferable high rate performance higher.So as to turn into major scientific researches
One of study hotspot problem of institutes and company, and great sizable application value.
However, content of the selenium in the composite of all these selenium positive poles is no greater than 70%, this is caused with whole the moon
The quality of pole is come if calculating, its electrode quality makes us very dissatisfied.The preparation method of these composites such as selenium carbon is usual simultaneously
It is required for consuming plenty of time and substantial amounts of energy.Therefore, it is badly in need of a kind of new simple energy-efficient method to prepare selenium electricity
Pole material.However, many selenides of intermediate product high-valence state that selenium electrode is generated in electric discharge and charging process are soluble in electrolyte,
Cause the loss of elemental selenium.Additionally, also there is shuttle effect, self discharge effect, battery pole in charge and discharge process in lithium selenium cell
The problems such as changing serious, volumetric expansion, the dissolving of negative pole lithium and form SEI films and Li dendrite.
In recent years, the material with excellent electric conductivity and fixed property is added in electrode material, can be further carried
The chemical property of selenium high, the positive electrode of lithium selenium cell is prepared for example with porous carbon materials composite selenium, can so be reduced
The dissolving of selenium simple substance, while selenium can reduce the contact with electrolyte to avoid active component in being scattered in the hole of porous carbon
It is lost in, the cycle performance of lithium selenium cell is improved so as to reach.But, such method still suffers from amount of activated component and electrolyte
Contact, simultaneously for the selenium carbon composite of high capacity selenium, its porous carbon surface can remain substantial amounts of active component selenium, can still make
Selenium dissolving in part in the electrolytic solution, thus cannot play a part of protection and to the abundant of active material to active component completely
Utilize.Meanwhile, the positive electrode of the lithium selenium cell that the method that above-mentioned tradition is coated is prepared needs conductive agent and binding agent, makes
Preparation Method is cumbersome.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation side of lithium selenium cell positive electrode
Method, the lithium selenium cell positive electrode for preparing of preparation method of the lithium selenium cell positive electrode that the present invention is provided is without conductive agent
With binding agent and with excellent charging and discharging capacity and cycle performance.
The invention provides a kind of plating solution for electroplating selenium, including：
Preferably, the selenous acid or selenite are selected from selenium dioxide, selenous acid, potassium selenite, sodium selenite, sub- selenium
One or more in sour calcium, magnesium selenite and lithium selenite；The electrolytic salt is selected from sodium chloride, potassium chloride, potassium sulfate, sulphur
One or more in sour sodium, potassium nitrate and sodium nitrate；The pH adjusting agent is selected from NaOH, potassium hydroxide and ammoniacal liquor
One or more；The pH buffer is selected from Potassium Hydrogen Phthalate, phosphate, acetic acid, sodium acetate, citric acid and citrate
One or more；The surfactant is selected from polyvinylpyrrolidone, PEO, Aethoxy Sklerol, octyl phenyl polyoxy
One or more in vinethene and cetyl trimethylammonium bromide.
The invention provides a kind of preparation method of lithium selenium cell positive electrode, comprise the following steps：
A) selenous acid or selenite, electrolytic salt, pH adjusting agent, pH buffer, surfactant and water are mixed, is obtained
To mixed liquor；
B) mixed liquor is electroplated under 15~60 DEG C of temperature conditionss in substrate, lithium selenium cell positive electrode is obtained.
Preferably, the step B) also include after plating the material that will be obtained after plating soaked on carbon material dispersion liquid,
Drying obtains the lithium selenium cell positive electrode of carbon coating.
Preferably, it is described
The concentration of selenous acid and its salt in mixed liquor is 5~500mmol/L；The electrolytic salt is dense in mixed liquor
It is 0.01~3mol/L to spend；Concentration of the pH buffer in mixed liquor is 0.01~2mol/L；The surfactant exists
Concentration in mixed liquor is 0.0001~0.2mol/L；The pH value of the mixed liquor is 1~9.
Preferably, the plating mode is selected from one or more in constant current, constant voltage, cyclic voltammetric and pulse.
Preferably, it is described
The electric current of constant current plating is 0.01~5mA, and electroplating time is 1min~5h；
The voltage of constant voltage plating is -0.3~-1v/cm2, electroplating time is 30s~2h；
The sweep limits of cyclic voltammetric plating is 0~-1v, 0.001~0.1v/s of sweep speed；
The current range of impulse method plating is 0.01~5mA.
Preferably, the base material be selected from nickel foam, foam gold, foamed iron, nickel sheet, iron plate and gold plaque in one kind or
It is several；The carbon material be selected from CMK, single wall CNT, many wall CNT, Graphene, graphene oxide, CNF, activated carbon, fullerene with
One or more in MOFs；The concentration of the carbon material dispersion liquid is 0.1~5mg/mL, and soak time is 5s~24h.
The invention provides a kind of lithium selenium cell positive electrode, the preparation method as described in above-mentioned technical proposal is prepared into
Arrive.
The invention provides a kind of lithium selenium cell, positive electrode of its positive pole as described in above-mentioned technical proposal is obtained.
Compared with prior art, the invention provides a kind of preparation method of lithium selenium cell positive electrode, including following step
Suddenly：A) selenous acid or selenite, electrolytic salt, pH adjusting agent, pH buffer, surfactant and water are mixed, is mixed
Close liquid；B) mixed liquor is electroplated under 15~60 DEG C of temperature conditionss in substrate, lithium selenium cell positive electrode is obtained.The present invention
Using specific electroplate liquid, coordinate specific electroplating parameter, the plating selenium layer that purity is high and crystallite dimension is small is prepared, while can
Obtain the structure of the different-shapes such as needle-like, island, mixed and disorderly pointed, bamboo shoots shape, loose structure.The material that the method is prepared can
To be directly used in lithium selenium cell, without adding any conductive agent and binding agent.The load capacity of selenium can be by control simultaneously
Electroplating time, plating current potential and surface current are controlled well.The preparation method system of the lithium selenium cell positive electrode that the present invention is provided
The standby lithium selenium cell positive electrode for obtaining has excellent charging and discharging capacity and cycle performance.The method of the present invention is applied to height
Carry on the secondary lithium selenium cell material of selenium amount, can preferably improve the charging and discharging capacity and cycle performance of its material.
Brief description of the drawings
Fig. 1 for the method for the plating selenium provided in the embodiment of the present invention 1 electroplate the scanning electricity of the Se@Ni materials of acquisition
Mirror photo；
Fig. 2 for the method for the plating selenium provided in the embodiment of the present invention 1 electroplate the friendship of the Se@Ni battery materials of acquisition
Flow impedance collection of illustrative plates；
Fig. 3 electroplate following for the Se@Ni battery materials of acquisition for the method for the plating selenium provided in the embodiment of the present invention 1
Ring volt-ampere collection of illustrative plates；
Fig. 4 exists for the Se@Ni battery materials that the method for the plating selenium provided in the embodiment of the present invention 1 electroplate acquisition
First charge-discharge curve map under 0.1C multiplying powers；
Fig. 5 exists for the Se@Ni battery materials that the method for the plating selenium provided in the embodiment of the present invention 1 electroplate acquisition
The charging and discharging curve figure of the circle of circulation 100 under 0.1C multiplying powers；
Fig. 6 exists for the Se@Ni battery materials that the method for the plating selenium provided in the embodiment of the present invention 1 electroplate acquisition
The charging and discharging curve figure of the circle of circulation 200 under 0.5C multiplying powers；
Fig. 7 for the method for the plating selenium provided in the embodiment of the present invention 1 electroplate the Raman light of the Se@Ni materials of acquisition
Spectrogram is composed；
Fig. 8 for the method for the plating selenium provided in the embodiment of the present invention 2 electroplate the scanning electricity of the Se@Ni materials of acquisition
Mirror photo；
Fig. 9 for the method for the plating selenium provided in the embodiment of the present invention 2 electroplate the friendship of the Se@Ni battery materials of acquisition
Flow impedance collection of illustrative plates；
Figure 10 electroplate the Se@Ni battery materials of acquisition for the method for the plating selenium provided in the embodiment of the present invention 2
Cyclic voltammetric collection of illustrative plates；
Figure 11 exists for the Se@Ni battery materials that the method for the plating selenium provided in the embodiment of the present invention 2 electroplate acquisition
First charge-discharge curve map under 0.1C multiplying powers；
Figure 12 exists for the Se@Ni battery materials that the method for the plating selenium provided in the embodiment of the present invention 2 electroplate acquisition
The charging and discharging curve figure of the circle of circulation 100 under 0.1C multiplying powers；
Figure 13 exists for the Se@Ni battery materials that the method for the plating selenium provided in the embodiment of the present invention 2 electroplate acquisition
The charging and discharging curve figure of the circle of circulation 200 under 0.5C multiplying powers；
Figure 14 electroplate sweeping for the GO@Se@Ni materials of acquisition for the method for the plating selenium provided in the embodiment of the present invention 3
Retouch electromicroscopic photograph；
Figure 15 for the method for the plating selenium provided in the embodiment of the present invention 3 electroplate the C of the GO@Se@Ni materials of acquisition,
The distribution map of O, Ni and Se each element；
Figure 16 is that the method for the plating selenium of offer in the embodiment of the present invention 3 carries out nickel in the GO@Se@Ni materials for electroplate acquisition
Net, the Raman spectrogram of Se@Ni and GO@Se@Ni materials；
Figure 17 for the method for the plating selenium provided in the embodiment of the present invention 3 electroplate the GO@Se@Ni battery materials of acquisition
First charge-discharge curve map under 0.1C multiplying powers；
Figure 18 for the method for the plating selenium provided in the embodiment of the present invention 3 electroplate the GO@Se@Ni battery materials of acquisition
The charging and discharging curve figure of the circle of circulation 100 under 0.1C multiplying powers.
Specific embodiment
The invention provides a kind of plating solution for electroplating selenium, including：
The plating solution of the plating selenium that the present invention is provided, including 0.645~102.5 weight portion selenous acid or selenite；It is preferred that
Including 10~80 weight portion selenous acid or selenite；More preferably include 15~60 weight portion selenous acid or selenite；It is optimal
Choosing includes 25~50 weight portion selenous acid or selenite.
In the present invention, the selenous acid or selenite are preferably selected from selenium dioxide, selenous acid, potassium selenite, sub- selenium
One or more in sour sodium, calcium selenite, magnesium selenite and lithium selenite；It is more preferably selected from selenous acid, potassium selenite, sub- selenium
One or more in sour sodium and calcium selenite；Most preferably selenous acid.
The plating solution of the plating selenium that the present invention is provided includes the electrolytic salt of 0.585~426 weight portion；Preferably include 3.5~
The electrolytic salt of 350 weight portions；More preferably include the electrolytic salt of 15~300 weight portions；Most preferably include 25~280 weight portions
Electrolytic salt.
Electrolytic salt of the present invention is preferably selected from sodium chloride, potassium chloride, potassium sulfate, sodium sulphate, potassium nitrate and sodium nitrate
In one or more；It is more preferably selected from one or more in sodium chloride, potassium chloride, potassium sulfate and sodium sulphate.
The plating solution of the plating selenium that the present invention is provided includes the pH adjusting agent of 0.01~5.6 weight portion；Preferably include 0.1~5
The pH adjusting agent of weight portion；More preferably include the pH adjusting agent of 0.5~4 weight portion.
PH adjusting agent of the present invention is preferably selected from one or more in NaOH, potassium hydroxide and ammoniacal liquor；It is more excellent
Choosing is selected from one or more in NaOH or potassium hydroxide.
The plating solution of plating selenium of the present invention includes the pH buffer of 0.01~400 weight portion；Preferably include 0.1~300
The pH buffer of weight portion；More preferably include the pH buffer of 1~200 weight portion.
PH buffer of the present invention be preferably selected from Potassium Hydrogen Phthalate, phosphate, acetic acid, sodium acetate, citric acid and
One or more in citrate；It is more preferably selected from one or more in Potassium Hydrogen Phthalate, phosphate and acetic acid.
The plating solution of the plating selenium that the present invention is provided includes the surfactant of 0.05~200 weight portion；Preferably include 0.1~
The surfactant of 150 weight portions；More preferably include the surfactant of 1~100 weight portion.
Surfactant of the present invention is preferably selected from polyvinylpyrrolidone, PEO, Aethoxy Sklerol, octyl phenyl
One or more in APEO and cetyl trimethylammonium bromide；It is more preferably selected from polyvinylpyrrolidone, polycyclic oxygen
One or more in ethane, Aethoxy Sklerol and octyl phenyl polyoxyethylene ether.
The plating solution of the plating selenium that the present invention is provided includes the water of 500~1000 weight portions；Preferably include 600~1000 weight
The water of part；More preferably include the water of 800~1000 weight portions.
The preparation method of above-mentioned plating solution of the present invention, is preferably specially：
By selenous acid or selenite, electrolytic salt, pH adjusting agent, pH buffer, the surfactant of above-mentioned weight portion
With water mixing, plating solution is obtained.
The present invention is not defined for the concrete mode of the mixing, mode well known to those skilled in the art.
The present invention is not defined for the hybrid mode, after preferably first selenous acid or selenite and water are mixed, then with electricity
Solution matter salt, pH adjusting agent, pH buffer, surfactant mixing.
The invention provides a kind of preparation method of lithium selenium cell positive electrode, comprise the following steps：
A) selenous acid or selenite, electrolytic salt, pH adjusting agent, pH buffer, surfactant and water are mixed, is obtained
To mixed liquor；
B) mixed liquor is electroplated under 15~60 DEG C of temperature conditionss in substrate, lithium selenium cell positive electrode is obtained.
The preparation method of the lithium selenium cell positive electrode that the present invention is provided is first by selenous acid or selenite, electrolyte
The mixing of salt, pH adjusting agent, pH buffer, surfactant and water, obtains mixed liquor.
Wherein, the concentration of the selenous acid and its salt in mixed liquor is preferably 5~500mmol/L；More preferably 50~
450mmol/L；Most preferably 100~400mmol/L；
Concentration of the electrolytic salt in mixed liquor is preferably 0.01~3mol/L；More preferably 0.05~2.5mol/
L；Most preferably 0.1~2mol/L；
Concentration of the pH buffer in mixed liquor is preferably 0.01~2mol/L；More preferably 0.05~1mol/L；
Most preferably 0.1~0.5mol/L；
Concentration of the surfactant in mixed liquor is preferably 0.0001~0.2mol/L；More preferably 0.001~
0.08mol/L；Most preferably 0.01~0.05mol/L.
In the present invention, pH adjusting agent is added to cause that the pH value of the mixed liquor is preferably 1~9.
The above-mentioned mixed liquor being mixed to get as electroplate liquid.The present invention is not defined for the hybrid mode, preferably
After first mixing selenous acid or selenite and water, then mixed with electrolytic salt, pH adjusting agent, pH buffer, surfactant
Close.
Mixed liquor is electroplated under 15~60 DEG C of temperature conditionss in substrate, selenium coating is obtained.As lithium selenium cell is being just
Pole material.It is preferred that be specially electroplating mixed liquor in substrate under 20~55 DEG C of temperature conditionss, selenium coating is obtained.
The substrate is preferably surface treated substrate, and surface treatment mode of the present invention is preferably specially：
Processed with solvent supersonic, the solvent is preferably one or more of acetone, ethanol, hydrochloric acid and nitric acid.
More preferably it is specially：10~15min of ultrasound in acetone；10~15min of ultrasound in ethanol；Then 2~
10~15min of ultrasound in the hydrochloric acid of 3mol/L；20~30min is soaked in last hydrochloric acid again；Then 20~24h of vacuum drying is final
The substrate being surface-treated.
Base material of the present invention is preferably selected from nickel foam, foam gold, foamed iron, nickel sheet, iron plate and gold plaque
Plant or several.
In the present invention, the plating mode is selected from the one kind or several in constant current, constant voltage, cyclic voltammetric and pulse
Kind.
It is preferred that being specially：
The electric current of the constant current plating is preferably 0.01~5mA, more preferably 0.05~4.5mA；Most preferably 0.3~
4.0mA；The electroplating time is preferably 1min~5h；More preferably 15min~4.5h；Most preferably 30min~4h；
The voltage of the constant voltage plating is preferably -0.3~-1v/cm2, more preferably -0.50~-0.8v/cm2, it is optimal
Elect -0.53~-0.7v/cm as2；The electroplating time is preferably 30s~2h；More preferably 1min~1.5h；Most preferably
30min~1.2h；
The sweep limits of the cyclic voltammetric plating is preferably 0~-1v, sweep speed preferably 0.001~0.1v/s；It is more excellent
Elect 0.01~0.08v/s as；The electroplating time is preferably 12.5s~100s；
The current range of the impulse method plating is preferably 0.01~5mA；More preferably 0.1~4.5mA；Most preferably
0.5~3.0mA；The electroplating time is preferably 30min~3h.
Also obtained including being soaked the material obtained after plating on carbon material dispersion liquid, being dried after preferred plating of the invention
The lithium selenium cell positive electrode of carbon coating.
More preferably it is specially：The selenium coating that will be obtained after plating soaks on carbon material dispersion liquid, dry and obtain carbon coating
Lithium selenium cell positive electrode.
In the present invention, the carbon material is preferably selected from CMK, single wall CNT, many wall CNT, Graphene, graphene oxide,
One or more in CNF, activated carbon, fullerene and MOFs；More preferably CMK, single wall CNT, many wall CNT, Graphene, oxidation
Graphene, CNF and activated carbon, in one or more；
The concentration of the carbon material dispersion liquid is preferably 0.1~5mg/mL, more preferably 0.5~3mg/mL, the immersion
Time is preferably 5s~24h；More preferably 1min~10h；Most preferably 1min~3h；The immersion number of times is preferably 2~5
It is secondary.
The temperature of the drying is preferably 60~100 DEG C；The drying time is preferably 20~24h.
The present inventor it is creative selenium electrode material is prepared instead of traditional chemical method using electro-plating method first.By this
Electroplate liquid and method can prepare the plating selenium layer that purity is high and crystallite dimension is small, while needle-like is can obtain, island, mixed and disorderly point
The structure of the different-shapes such as shape, bamboo shoots shape, loose structure.Processed through carbon material by above-mentioned resulting materials, performance is more preferably.This
The material that method is prepared is used directly for lithium selenium cell, without adding any conductive agent and binding agent.While selenium
Load capacity can be by controlling electroplating time, plating current potential and surface current be controlled well.The method is also highly suitable for application
In on the secondary lithium selenium cell material that height carries selenium amount, the charging and discharging capacity and cycle performance of its material can be preferably improved.
The invention provides a kind of lithium selenium cell positive electrode, the preparation method as described in above-mentioned technical proposal is prepared into
Arrive.
The invention provides a kind of lithium selenium cell, positive electrode of its positive pole as described in above-mentioned technical proposal is obtained.
It is negative plate, the LiCF of 0.5mol/L that lithium selenium cell of the present invention uses lithium piece3SO3Coordinate 0.5mol/L
LiNO3Mixed solution (DME:DOL=1：1 (V/V)) it is electrolyte, polypropylene of the barrier film from model Celgard 2400
Microporous barrier, is assembled into CR2032 simulated batteries；
Above-mentioned institute's packed battery is connected into electrochemical workstation, discharge and recharge instrument carries out electrochemical property test.
The invention provides a kind of preparation method of lithium selenium cell positive electrode, comprise the following steps：A) by selenous acid or
The mixing of selenite, electrolytic salt, pH adjusting agent, pH buffer, surfactant and water, obtains mixed liquor；B) by mixed liquor
Electroplated in substrate under 15~60 DEG C of temperature conditionss, obtain lithium selenium cell positive electrode.The present invention is using specific plating
Liquid, coordinates specific electroplating parameter, prepares the plating selenium layer that purity is high and crystallite dimension is small, while needle-like is can obtain, island,
The structure of the different-shapes such as mixed and disorderly pointed, bamboo shoots shape, loose structure.The material that the method is prepared is used directly for lithium selenium
Battery, without adding any conductive agent and binding agent.The load capacity of selenium can be by controlling electroplating time, plating electricity simultaneously
Position and surface current are controlled well.The lithium selenium cell that the preparation method of the lithium selenium cell positive electrode that the present invention is provided is prepared
Positive electrode has excellent charging and discharging capacity and cycle performance.The method of the present invention is applied to the secondary lithium selenium for carrying selenium amount high
On battery material, the charging and discharging capacity and cycle performance of its material can be preferably improved.
In order to further illustrate the present invention, the plating solution of the plating selenium for providing the present invention with reference to embodiments, lithium selenium electricity
Pond positive electrode and lithium selenium cell are described in detail.
Embodiment 1
It is the selenium dioxide of the electronic balance weighing 1.11g of 0.00001g using precision；It is 0.00001g's using precision
The potassium chloride of electronic balance weighing 1.86g；It is the potassium hydroxide of the electronic balance weighing 0.02g of 0.00001g using precision；Profit
With the polyvinylpyrrolidone of the electronic balance weighing 0.1g that precision is 0.00001g；It is the electronics day of 0.00001g using precision
The flat Potassium Hydrogen Phthalate for weighing 3.75g.An addition 100ml is blended in by the above-mentioned medicine for claiming is full and uniform successively
In the square opening beaker of the 200ml capacity of deionized water, so that electroplate liquid is obtained.
0.5mm is thick, the strip nickel foam of length and width 6*1cm ultrasound 10min in acetone, in ethanol ultrasound 10min,
The ultrasound 10min in the dilute hydrochloric acid solution of the 3mol/L for preparing, soaks 30min in above-mentioned hydrochloric acid, is vacuum dried 24h to obtain
Obtain the good foam nickel base in the treated top layer in surface.To electrode titanium net device ultrasound 10min in acetone, in ethanol
Ultrasonic 10min, the ultrasound 5min in the salpeter solution for preparing, soak 30min in above-mentioned salpeter solution, are vacuum dried 24h
With obtain surface it is clean to electrode assembly.
Above-mentioned resulting solution is placed in 35 DEG C of water bath with thermostatic control kettles；Connect into electroplanting device, constant potential electroplating voltage is set
Parameter is -0.53v, and electroplating time is 40min；So that material requested is obtained.
Plated material clear water is rinsed, is vacuum dried 24h to obtain good plating selenium cell material.Above-mentioned material is entered
Row sem test, as a result as shown in figure 1, the method that Fig. 1 is the plating selenium of offer in the embodiment of the present invention 1 carries out plating and obtains
The stereoscan photograph of the Se@Ni materials for obtaining；More uniform graininess selenium plating has been obtained after electroplating as seen from Figure 1
Layer.Above-mentioned gained plating selenium material is directly used in cell positive material.It is negative plate, the LiCF of 0.5mol/L to use lithium piece3SO3
Coordinate 0.5mol/L LiNO3Mixed solution (DME:DOL=1：1 (V/V)) it is electrolyte, barrier film selects model Celgard
2400 microporous polypropylene membrane, is assembled into CR2032 simulated batteries；Above-mentioned institute's packed battery is connected into electrochemical workstation, discharge and recharge
Instrument carries out electrochemical property test.As shown in Fig. 2~Fig. 8, wherein Fig. 2 is the plating selenium of offer in the embodiment of the present invention 1 to result
Method carry out electroplate acquisition Se@Ni battery materials ac impedance spectroscopy；Plating has obtained more uniform selenium coating, and
And it is good as the impedance behavior of positive electrode；Fig. 3 is that the method for the plating selenium of offer in the embodiment of the present invention 1 is electroplated
The cyclic voltammetric collection of illustrative plates of the Se Ni battery materials of acquisition；In cyclic voltammetric, multigroup reduction peak 2.18v, 1.92v and 1.35v
Meet many selenides LiSen (n ＞ 4) that Se simple substance in multistep electrochemical reaction is reduced into high-order, intermediate product enters one afterwards
Step is reduced into Li2Se2And LiSe2, two oxidation peaks appear in 2.3v and 1.89v also complies with LiSe2It is oxidized to many selenizings
Thing, is further oxidized to the process of Se simple substance.Fig. 4 is that the method for the plating selenium of offer in the embodiment of the present invention 1 is electroplated
First charge-discharge curve map of the Se@Ni battery materials of acquisition under 0.1C multiplying powers；As seen from Figure 4, first circle electric discharge specific volume
It is 336mah/g to measure, and charging specific volume 375mah/g；Fig. 5 is that the method for the plating selenium of offer in the embodiment of the present invention 1 carries out electricity
Plate obtain Se@Ni battery materials circulate under 0.1C multiplying powers 100 enclose charging and discharging curve figures in cycle charge-discharge, 0.1c times
Specific capacity is 122mah/g after 100 circles under rate；Fig. 6 is obtained for the method for the plating selenium provided in the embodiment of the present invention 1 carries out plating
The Se@Ni battery materials for obtaining circulate the charging and discharging curve figures of 200 circles under 0.5C multiplying powers；After the circle of circulation 200 under 0.5c multiplying powers
Specific capacity be 68mah/g；Fig. 7 for the method for the plating selenium provided in the embodiment of the present invention 1 electroplate the Se@Ni materials of acquisition
The Raman spectrum collection of material.
Embodiment 2
Using the selenium dioxide of the electronic balance weighing 1.11g that precision is 0.00 1g；It is the electronics of 0.001g using precision
Balance weighs the potassium chloride of 1.86g；It is the potassium hydroxide of the electronic balance weighing 0.02g of 0.001g using precision；Using precision
It is the PEO of the electronic balance weighing 0.05g of 0.00001g；It is the electronic balance weighing of 0.00001g using precision
The citric acid of 2.15g.
A 200ml capacity for addition 100ml deionized waters is blended in by the above-mentioned medicine for claiming is full and uniform successively
Square opening beaker be obtained electroplate liquid；
0.5mm is thick, the strip nickel foam of length and width 6*1cm ultrasound 10min in acetone, in ethanol ultrasound 10min,
The ultrasound 10min in the dilute hydrochloric acid solution of the 3mol/L for preparing, soaks 30min in above-mentioned hydrochloric acid, is vacuum dried 24h to obtain
Obtain the good foam nickel base in the treated top layer in surface.
To electrode titanium net device ultrasound 10min in acetone, ultrasound 10min in ethanol, in the salpeter solution for preparing
Middle ultrasonic 5min, soaks 30min in above-mentioned salpeter solution, vacuum drying 24h with obtain surface it is clean to electrode assembly.
Above-mentioned resulting solution is placed in 35 DEG C of water bath with thermostatic control kettles, is connected into electroplanting device, constant potential electroplating voltage is set
Parameter is 0.5mA/cm2, electroplating time is 3h；So that material requested is obtained.Plated material vacuum drying 24h is good to obtain
Plating selenium cell material；By above-mentioned material be scanned Electronic Speculum test, as a result as shown in figure 8, Fig. 8 be the embodiment of the present invention 2 in carry
The method of the plating selenium of confession carries out the stereoscan photograph of the Se@Ni materials for electroplating acquisition；Plating as seen from Figure 8 is obtained
The selenium coating of the good form of spherical particles of uniformity；
Above-mentioned gained plating selenium material is directly used in cell positive material.It is negative plate to use lithium piece, 0.5mol/L's
LiCF3SO3Coordinate 0.5mol/L LiNO3Mixed solution (DME:DOL=1：1 (V/V)) it is electrolyte, barrier film selects model
The microporous polypropylene membrane of Celgard 2400, is assembled into CR2032 simulated batteries；Above-mentioned institute's packed battery is connected into electrochemical operation
Stand, discharge and recharge instrument carries out electrochemical property test.Result as shown in Fig. 9~Figure 13, wherein, Fig. 9 be the embodiment of the present invention 2 in carry
The method of the plating selenium of confession carries out the ac impedance spectroscopy of the Se@Ni battery materials for electroplating acquisition；As seen from Figure 9, electroplate
The selenium coating of more uniform form of spherical particles has been obtained, and it is preferable as the impedance behavior of lithium selenium cell positive electrode；
The method of the plating selenium provided in Figure 10 embodiment of the present invention 2 carries out the cyclic voltammogram of the Se@Ni battery materials for electroplating acquisition
Spectrum；As seen from Figure 10, multigroup reduction peak 2.18v, 1.98v and 1.67v just meet Se simple substance in multistep electrochemical reaction
Many selenides LiSen (n ＞ 4) of high-order are reduced into, intermediate product is further reduced into Li afterwards2Se2And LiSe2, two
Oxidation peak appears in 2.3v and 1.82v and also complies with LiSe2 and is oxidized to many selenides, is further oxidized to the mistake of Se simple substance
Journey；Figure 11 is that the method for the plating selenium of offer in the embodiment of the present invention 2 electroplate the Se@Ni battery materials of acquisition at 0.1C times
First charge-discharge curve map under rate；Found out by Figure 11, Figure 12 is that the method for the plating selenium of offer in the embodiment of the present invention 2 is carried out
Electroplate the charging and discharging curve figure that the Se@Ni battery materials for obtaining circulate 100 circles under 0.1C multiplying powers；In cycle charge-discharge,
Specific capacity is 126mah/g after 100 circles under 0.1c multiplying powers；Figure 13 is that the method for the plating selenium of offer in the embodiment of the present invention 2 is carried out
Electroplate the charging and discharging curve figure that the Se@Ni battery materials for obtaining circulate 200 circles under 0.5C multiplying powers；In cycle charge-discharge,
Specific capacity is 126mah/g after 100 circles under 0.1c multiplying powers.
Embodiment 3
Using the sodium selenite of the electronic balance weighing 1.73g that precision is 0.00 1g；It is the electronics of 0.001g using precision
Balance weighs the sodium sulphate of 3.8g；It is the NaOH of the electronic balance weighing 0.01g of 0.001g using precision；It is using precision
The Aethoxy Sklerol of the electronic balance weighing 0.052g of 0.001g；It is the acetic acid of the electronic balance weighing 0.08g of 0.001g using precision
Sodium；A square opening for the 200ml capacity of addition 100ml deionized waters is blended in by the above-mentioned medicine for claiming is full and uniform successively
Beaker is obtained electroplate liquid；
By 0.5mm thickness (6*1cm) nickel foam ultrasound 10min in acetone, ultrasound 10min in ethanol, what is prepared
Ultrasound 10min in the dilute hydrochloric acid solution of 3mol/L, soaks 30min in above-mentioned hydrochloric acid, and vacuum drying 24h is passed through with obtaining surface
The good foam nickel base in the top layer for the treatment of.To electrode titanium net device ultrasound 10min in acetone, ultrasound 10min in ethanol,
The ultrasound 5min in the salpeter solution for preparing, soaks 30min in above-mentioned salpeter solution, is vacuum dried 24h to obtain surface
It is clean to electrode assembly.
Above-mentioned resulting solution is placed in 40 DEG C of water bath with thermostatic control kettles；Connect into electroplanting device, constant current electroplating current is set
Parameter is 0.5mA/cm2, electroplating time is 3h；If by plated material 3 common 6h of Graphene soaking flushing of 2mg/mL；Enter one
Step is vacuum dried 24h to obtain good plating selenium cell material；By above-mentioned material be scanned Electronic Speculum test, as a result as Figure 14~
Shown in Figure 16, Figure 14 electroplate the GO@Se@Ni materials of acquisition for the method for the plating selenium provided in the embodiment of the present invention 3
Stereoscan photograph；Figure 15 for the method for the plating selenium provided in the embodiment of the present invention 3 electroplate the GO@Se@Ni materials of acquisition
The C of material, the distribution map of O, Ni and Se each element；Figure 16 is that the method for the plating selenium of offer in the embodiment of the present invention 3 is electroplated
Nickel screen in the GO@Se@Ni materials of acquisition, the Raman spectrogram of Se@Ni and GO@Se@Ni materials；Be can be seen that by Figure 14 and Figure 15
The laminar GO attachments of fold are coated on outer surface, and uniform by EDS power spectrums test result display Se, C, and O element
The surface for being distributed in nickel foam, while the Raman collection of illustrative plates of Figure 16 also demonstrate that the presence of GO clads, Se@Ni electrode materials exist
Coated after GO, occurred in that the peak of 1350cm-1 and 1580cm-1 again in Raman collection of illustrative plates.It is just to carbon atom lattice
Stretching vibration in the face of defect and carbon atom sp2 hydridization.
Above-mentioned gained plating selenium material is directly used in cell positive material.It is negative plate to use lithium piece, 0.5mol/L's
LiCF3SO3Coordinate 0.5mol/L LiNO3Mixed solution (DME:DOL=1：1 (V/V)) it is electrolyte, barrier film selects model
The microporous polypropylene membrane of Celgard 2400, is assembled into CR2032 simulated batteries.
Above-mentioned institute's packed battery is connected into electrochemical workstation, discharge and recharge instrument carries out electrochemical property test.
As shown in FIG. 17 and 18, wherein Figure 17 is that the method for the plating selenium of offer in the embodiment of the present invention 3 carries out electricity to result
Plate first charge-discharge curve map of the GO@Se@Ni battery materials for obtaining under 0.1C multiplying powers；Figure 18 is in the embodiment of the present invention 3
The GO@Se@Ni battery materials that the method for the plating selenium of offer electroplate acquisition circulate 100 discharge and recharges enclosed under 0.1C multiplying powers
Curve map；Be can be seen that compared to Se@Ni materials by Figure 17 and Figure 18, the GO@Se@Ni materials processed by GO dispersion liquids have
The first circle specific capacity very high of 648mah/g, and the circle of circulation 100 still has the specific capacity of 245mah/g under 0.1c multiplying powers
Keep.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. it is a kind of electroplate selenium plating solution, including：
2. plating solution according to claim 1, it is characterised in that the selenous acid or selenite are selected from selenium dioxide, sub-
One or more in selenic acid, potassium selenite, sodium selenite, calcium selenite, magnesium selenite and lithium selenite；The electrolytic salt
Selected from one or more in sodium chloride, potassium chloride, potassium sulfate, sodium sulphate, potassium nitrate and sodium nitrate；The pH adjusting agent is selected from
One or more in NaOH, potassium hydroxide and ammoniacal liquor；The pH buffer be selected from Potassium Hydrogen Phthalate, phosphate,
One or more in acetic acid, sodium acetate, citric acid and citrate；The surfactant be selected from polyvinylpyrrolidone,
One or more in PEO, Aethoxy Sklerol, octyl phenyl polyoxyethylene ether and cetyl trimethylammonium bromide.
3. a kind of preparation method of lithium selenium cell positive electrode, it is characterised in that comprise the following steps：
A) selenous acid or selenite, electrolytic salt, pH adjusting agent, pH buffer, surfactant and water are mixed, is mixed
Close liquid；
B) mixed liquor is electroplated under 15~60 DEG C of temperature conditionss in substrate, lithium selenium cell positive electrode is obtained.
4. preparation method according to claim 3, it is characterised in that the step B) also including after plating will be after plating
To material soaked on carbon material dispersion liquid, dry the lithium selenium cell positive electrode that obtains carbon coating.
5. preparation method according to claim 3, it is characterised in that described
The concentration of selenous acid and its salt in mixed liquor is 5~500mmol/L；Concentration of the electrolytic salt in mixed liquor is
0.01~3mol/L；Concentration of the pH buffer in mixed liquor is 0.01~2mol/L；The surfactant is in mixing
Concentration in liquid is 0.0001~0.2mol/L；The pH value of the mixed liquor is 1~9.
6. preparation method according to claim 3, it is characterised in that the plating mode is selected from constant current, constant voltage, follows
Ring volt-ampere and pulse in one or more.
7. preparation method according to claim 6, it is characterised in that described
The electric current of constant current plating is 0.01~5mA, and electroplating time is 1min~5h；
The voltage of constant voltage plating is -0.3~-1v/cm2, electroplating time is 30s~2h；
The sweep limits of cyclic voltammetric plating is 0~-1v, 0.001~0.1v/s of sweep speed；
The current range of impulse method plating is 0.01~5mA.
8. preparation method according to claim 4, it is characterised in that the base material is selected from nickel foam, foam gold, bubble
One or more in foam iron, nickel sheet, iron plate and gold plaque；The carbon material be selected from CMK, single wall CNT, many wall CNT, Graphene,
Graphene oxide, one or more in CNF, activated carbon, fullerene and MOFs；The concentration of the carbon material dispersion liquid is 0.1
~5mg/mL, soak time is 5s~24h.
9. a kind of lithium selenium cell positive electrode, it is characterised in that the preparation method system as described in claim 3~8 any one
It is standby to obtain.
10. a kind of lithium selenium cell, it is characterised in that its positive pole is obtained as the positive electrode described in claim 9.
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