CN106229498A - A kind of negative material being applicable to Water based metal ion battery and preparation method thereof - Google Patents
A kind of negative material being applicable to Water based metal ion battery and preparation method thereof Download PDFInfo
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- CN106229498A CN106229498A CN201610632608.5A CN201610632608A CN106229498A CN 106229498 A CN106229498 A CN 106229498A CN 201610632608 A CN201610632608 A CN 201610632608A CN 106229498 A CN106229498 A CN 106229498A
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- 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
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H—ELECTRICITY
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Abstract
The present invention relates to a kind of negative material being applicable to Water based metal ion battery and preparation method thereof, described negative material contains bismuth oxide, this negative material is nano bismuth oxide array film, i.e. it is made up of oriented growth bismuth oxide nanometer sheet in metallic substrates, bismuth oxide nanometer sheet Vertical Uniform dense distribution is on the metallic substrate, in array-like, or masking obtains on the metallic substrate after being mixed homogeneously with conductive additive, binding agent by bismuth oxide powder.The water system battery system that the negative material of the Water based metal ion battery that the present invention provides is suitable for is relatively wide, including aquo-lithium ion battery, water system sodium-ion battery, water system kalium ion battery, water system Magnesium ion battery, water system calcium ion battery, water system strontium ion battery, water system barium ions battery and water system aluminium ion battery etc..And negative material gained Water based metal ion battery capacity is big, charge and discharge platform good, electrochemical reversibility is high based on this.
Description
Technical field
The invention belongs to water system battery material technical field, be specifically related to a kind of be applicable to the negative of Water based metal ion battery
Pole material and preparation method thereof.
Background technology
Having benefited from the chemical property highlighted, organic bath lithium ion battery has obtained studying widely and answering in recent years
With.But organic bath exists bigger potential safety hazard, and price is relatively costly, encapsulation is required higher, there is also lithium ion mobility
The inherent shortcoming such as speed is slow and environmental pollution is high.In order to solve these problems of organic bath, Canada Moli Energy
Company's (patent No. W095/20470) proposes the concept of the aquo-lithium ion battery using aqueous solution as electrolyte, with the most green
Environmental protection, water the safest, the most continuable are solvent.On this basis, Fudan University (patent publication No. CN 101154745A) carries
Supply a kind of based on the carbon intercalation compound LiTi of cladding2(PO4)3The aquo-lithium ion secondary cell of nucleocapsid structure negative material,
Further increase the combination property of aquo-lithium ion battery.
In prior art, the study general about Water based metal ion battery is all carried out around lithium ion battery.But, one
Aspect, nature lithium amount of storage is limited, along with the developing rapidly of lithium related industries, the exhaustion of lithium can arrive sooner or later；The opposing party
Face, by the steady potential window limit that aqueous solution is narrower, even if in more ripe aquo-lithium ion battery, has excellent electricity
The negative material of chemical property is the most rare, it is thus well known that NASICON type titanium phosphate lithium and titanium phosphate sodium, although have relatively
Good charge and discharge platform, suitable removal lithium embedded current potential and longer cycle life, its capacity the most extremely limited (< 150mAh/g).
Therefore, this kind of following possible replacement lithium ion of non-lithium ion battery (such as sodium-ion battery, Magnesium ion battery, aluminium ion battery etc.)
The novel water system battery system of battery gradually demonstrates important scientific research and industrial application value.On the one hand, fit at present
Negative material for Water based metal ion battery field is fewer, and existing negative material is normally only applicable to specifically
Water based metal ion battery, therefore, it is necessary to research is widely portable to the negative material of multiple Water based metal ion battery.
Summary of the invention
The technical problem to be solved is for above-mentioned deficiency present in prior art, it is provided that a kind of capacity
Greatly, have extended cycle life, charge and discharge platform is good, be applicable to negative material and the preparation side thereof of multiple Water based metal ion battery systems
Method.
For solving above-mentioned technical problem, present invention provide the technical scheme that
Thering is provided a kind of negative material being applicable to Water based metal ion battery, described negative material contains bismuth oxide.
By such scheme, described negative material is nano bismuth oxide array film, and it is by oriented growth oxygen in metallic substrates
Changing bismuth nanometer sheet to constitute, described bismuth oxide nanometer sheet Vertical Uniform dense distribution is on the metallic substrate, in array-like.
Preferably, described metallic substrates is titanium sheet.
Preferably, described bismuth oxide nanometer sheet thickness is 10-30nm.
By such scheme, the preparation method of described nano bismuth oxide array film is: the titanium sheet of clean surface is placed in
In the bismuth-containing precursor liquid that ethylene glycol and acetone obtain as mixed solvent preparation, through hydro-thermal reaction prepare be applicable to Water based metal from
The negative material of sub-battery.
Preferably, in described bismuth-containing precursor liquid, five liquid glauber salt acid bi concns are 0.03-0.04g/mL.
By such scheme, described negative material mixed homogeneously with conductive additive, binding agent by bismuth oxide powder after at gold
Belong to masking in substrate to obtain.
By such scheme, cathode material preparation method step is as follows:
1) bismuth oxide powder is prepared: obtain bismuth-containing precursor liquid, before bismuth-containing using ethylene glycol and acetone as mixed solvent preparation
Drive liquid and obtain bismuth oxide powder through hydro-thermal reaction post processing again；
2) bismuth oxide powder, conductive additive, binding agent being added in solvent, abundant ball milling prepares slurry, then by institute
Obtain slurry to be coated uniformly in titanium sheet, obtain being applicable to the negative of Water based metal ion battery by tablet machine compression process again after drying
Pole material.
Preferably, described ethylene glycol and acetone volume ratio are 1:1-2.
By such scheme, described bismuth-containing precursor liquid is dissolved in mixed solvent by five water bismuth nitrate and obtaining；Described hydro-thermal reaction
Temperature is 120-180 DEG C, and the response time is 3-8h.
By such scheme, described conductive additive is white carbon black, Graphene or CNT, binding agent be Kynoar or
Politef, wherein bismuth oxide powder accounts for the mass ratio of negative material is 60-80%, and conductive additive accounts for the matter of negative material
Amount ratio is 5-20%, and it is 5-20% that binding agent accounts for the mass ratio of negative material.
The present invention also provides for a kind of Water based metal ion battery, the composition of described Water based metal ion battery include positive pole,
Negative pole and electrolyte, described negative pole contains above-mentioned negative material.
By such scheme, described Water based metal ion battery includes aquo-lithium ion battery, water system sodium-ion battery, water system
Kalium ion battery, water system Magnesium ion battery, water system calcium ion battery, water system strontium ion battery, water system barium ions battery and water system
The mixing water system ion battery of the one or more than one in aluminium ion battery.
By such scheme, described electrolyte is the mixed of one or more of the sulfate of solubility, nitrate and chlorate
Heshui solution.
Preferably, the electrolyte of described Water based metal ion battery is lithium sulfate, lithium chloride, lithium nitrate, sodium sulfate, chlorine
Change sodium, sodium nitrate, potassium sulfate, potassium chloride, potassium nitrate, magnesium chloride, magnesium nitrate, calcium chloride, calcium nitrate, strontium chloride, strontium nitrate, chlorine
Changing one or more the aqueous solution in barium, barium nitrate, aluminum nitrate, pH value of water solution is 2.0-8.0, and cation concn is
0.5-10mol/L。
By such scheme, described positive pole is added conductive agent, binding agent by positive electrode and is coated uniformly on collector again
Arrive.
In the present invention, positive electrode is material based on redox reaction, concretely can embed lithium, sodium, potassium, magnesium,
One or more mixed oxide in the oxides such as calcium, strontium, barium and aluminum ions Mn, Co, Ni, Fe or conducting polymer
Thing, or positive electrode based on redox reaction.
In the present invention, the collector of positive and negative electrode can be material with carbon element, metallic nickel, Titanium, stainless steel foil etc. or porous
Mesh substrate.
The novel water system chargeable battery electrode material of the present invention is the breakthrough in Water based metal ion battery field, it is adaptable to
The preparation technology of various electrodes, such as film, slurry and press mold etc..
Nano bismuth oxide array film prepared by the present invention or bismuth oxide powder electrode, and then prepare Water based metal ion-conductance
Pond, energy density (the 78Wh kg of gained Water based metal ion battery systems-1) higher than the most most Water based metal ion-conductances
Pond (≤50Wh kg-1), and owing to bismuth oxide Water based metal ion battery has good charge and discharge platform, battery can have surely
Fixed output voltage.
The beneficial effects of the present invention is: the invention provides the negative pole material of a kind of novel Water based metal ion battery
Material, its water system battery system being suitable for is relatively wide, including aquo-lithium ion battery, water system sodium-ion battery, water system kalium ion battery,
Water system Magnesium ion battery, water system calcium ion battery, water system strontium ion battery, water system barium ions battery and water system aluminium ion battery
Deng.And negative material gained Water based metal ion battery capacity is big, charge and discharge platform good, electrochemical reversibility is high based on this.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the nano bismuth oxide array film prepared by the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope shape appearance figure of the nano bismuth oxide array film prepared by embodiment 1；
Fig. 3 is the constant current charge-discharge curve in 18 kinds of solution of the nano bismuth oxide array film prepared by embodiment 1；
Fig. 4 is the negative material prepared by bismuth oxide powder in embodiment 2 circulation in sodium nitrate solution and charge and discharge
Electricity curve chart；
Fig. 5 is the charging and discharging curve of the battery prepared by embodiment 4；
Fig. 6 is the discharge curve under different electric current densities of the battery prepared by embodiment 5.
Detailed description of the invention
For making those skilled in the art be more fully understood that technical scheme, below in conjunction with the accompanying drawings the present invention is made into
One step describes in detail, but the present invention is not limited to following example.
Reagent in the following example and material, if without specified otherwise, obtain the most from commercial channels.
Embodiment 1
Preparation is applicable to the negative material of Water based metal ion battery: by the five water bismuth nitrate of 0.6g, 6mL ethylene glycol,
The titanium sheet that cleaned thickness is 50 μm is put in bismuth-containing precursor liquid as bismuth-containing precursor liquid in 30 minutes by the stirring of 12mL acetone,
It is placed in 20mL polytetrafluoroethylliner liner, then inner bag is loaded hydrothermal reaction kettle and seals, 160 DEG C of Water Under thermal responses 5
Hour, stop heating subsequently and be cooled to room temperature, by ethanol and deionized water rinsing sample surfaces residual solution, at titanium sheet collector
One layer of bismuth oxide film of superficial growth, is i.e. applicable to the negative material of Water based metal ion battery.The X-ray of bismuth oxide film is spread out
Penetrate collection of illustrative plates and see that Fig. 1, the scanning electron microscope image of negative material surface oxidation bismuth thin film are shown in Fig. 2, it is seen that gained negative material
For nano bismuth oxide array film, it is made up of oriented growth bismuth oxide nanometer sheet in titanium sheet, and bismuth oxide nanometer sheet thickness is 10-
12nm, described bismuth oxide nanometer sheet Vertical Uniform dense distribution is on the metallic substrate, in array-like.
The test negative material prepared by the present embodiment redox reversible in different aqueous solutions:
1. using negative material as working electrode, with metal platinized platinum for electrode, saturated calomel electrode as reference electrode,
Electrolyte is the lithium sulfate solution of 0.5mol/L, and pH value is 7.08.Sweeping under speed at 1mV/s, bismuth oxide discharge capacity is
320mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 248mAh/g.
2. using negative material as working electrode, with metal platinized platinum for electrode, saturated calomel electrode as reference electrode,
Electrolyte is the metabisulfite solution of 0.5mol/L, and pH value is 7.16.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
322mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 278mAh/g.
3. using negative material as working electrode, with metal platinized platinum for electrode, saturated calomel electrode as reference electrode,
Electrolyte is the potassium sulfate solution of 0.5mol/L, and pH value is 6.90.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
234mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 232mAh/g.
4. using negative material as working electrode, with metal platinized platinum for electrode, saturated calomel electrode as reference electrode,
Electrolyte is the lithium chloride solution of 1mol/L, and pH value is 7.03.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
183mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 234mAh/g.
5. using negative material as working electrode, with metal platinized platinum for electrode, saturated calomel electrode as reference electrode,
Electrolyte is the sodium chloride solution of 1mol/L, and pH value is 7.06.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
324mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 157mAh/g.
6. using negative material as working electrode, with metal platinized platinum for electrode, saturated calomel electrode as reference electrode,
Electrolyte is the Klorvess Liquid of 1mol/L, and pH value is 6.91.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
342mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 248mAh/g.
7. using negative material as working electrode, with metal platinized platinum for electrode, saturated calomel electrode as reference electrode,
Electrolyte is the lithium nitrate solution of 1mol/L, and pH value is 7.41.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
214mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 278mAh/g.
8. using negative material as working electrode, with metal platinized platinum for electrode, saturated calomel electrode as reference electrode,
Electrolyte is the sodium nitrate solution of 1mol/L, and pH value is 7.26.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
235mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 255mAh/g.
9. using negative material as working electrode, with metal platinized platinum for electrode, saturated calomel electrode as reference electrode,
Electrolyte is the potassium nitrate solution of 1mol/L, and pH value is 7.10.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
317mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 186mAh/g.
10., using negative material as working electrode, with metal platinized platinum for electrode, saturated calomel electrode is as reference electricity
Pole, electrolyte is the magnesium chloride solution of 1mol/L, and pH value is 7.03.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
223mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 228mAh/g.
11. using negative material as working electrode, and with metal platinized platinum for electrode, saturated calomel electrode is as reference electricity
Pole, electrolyte is the magnesium nitrate solution of 1mol/L, and pH value is 6.62.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
84mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 156mAh/g.
12. using negative material as working electrode, and with metal platinized platinum for electrode, saturated calomel electrode is as reference electricity
Pole, electrolyte is the calcium chloride solution of 1mol/L, and pH value is 7.52.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
321mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 356mAh/g.
13. using negative material as working electrode, and with metal platinized platinum for electrode, saturated calomel electrode is as reference electricity
Pole, electrolyte is the calcium nitrate solution of 1mol/L, and pH value is 7.23.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
188mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 187mAh/g.
14. using negative material as working electrode, and with metal platinized platinum for electrode, saturated calomel electrode is as reference electricity
Pole, electrolyte is the strontium chloride solution of 1mol/L, and pH value is 7.00.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
104mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 106mAh/g.
15. using negative material as working electrode, and with metal platinized platinum for electrode, saturated calomel electrode is as reference electricity
Pole, electrolyte is the strontium nitrate solution of 1mol/L, and pH value is 7.41.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
177mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 164mAh/g.
16. using negative material as working electrode, and with metal platinized platinum for electrode, saturated calomel electrode is as reference electricity
Pole, electrolyte is the barium chloride solution of 1mol/L, and pH value is 7.27.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
331mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 165mAh/g.
17. using negative material as working electrode, and with metal platinized platinum for electrode, saturated calomel electrode is as reference electricity
Pole, electrolyte is saturated barium nitrate solution, and pH value is 7.46.Sweeping under speed at 1mV/s, the discharge capacity of bismuth oxide is
194mAh/g.Under the charging and discharging currents density of 0.5A/g, the discharge capacity of bismuth oxide is 258mAh/g.
18. using negative material as working electrode, and with metal platinized platinum for electrode, saturated calomel electrode is as reference electricity
Pole, electrolyte is the aluminum nitrate solution of 1mol/L, and pH value is 2.58.Under the charging and discharging currents density of 0.5A/g, bismuth oxide
Discharge capacity is 171mAh/g.
The pH value of above-mentioned 18 kinds of solution, the discharge capacity of cyclic voltammetry test and constant current charge-discharge test is shown in Table 1,
The constant current charge-discharge curve of various solution is shown in Fig. 3, illustrates that negative material prepared by the present embodiment is applicable to aquo-lithium ion electricity
Pond, water system sodium-ion battery, water system kalium ion battery, water system Magnesium ion battery, water system calcium ion battery, water system strontium ion electricity
Pond, water system barium ions battery and water system aluminium ion battery, have higher capacity, good charge and discharge platform.
Cyclic voltammetry (CV) capacity in different electrolytes of the pH value of table 1 different solutions and negative material and perseverance electricity
Stream charge and discharge electrical method (CD) capacity
Embodiment 2
Preparation is applicable to the negative material of Water based metal ion battery:
1) bismuth oxide powder is prepared: 0.6g five water bismuth nitrate, 6mL ethylene glycol, the stirring of 12mL acetone are placed on for 30 minutes
In 20mL polytetrafluoroethylliner liner, then inner bag is loaded in hydrothermal reaction kettle and seal, little 160 DEG C of Water Under thermal responses 5
Time, stop heating subsequently and be cooled to room temperature, with ethanol and deionized water at centrifuge stirring and washing sample, dry, obtain nanometer
Bismuth oxide powder；
2) negative material is prepared: by nano bismuth oxide powder, white carbon black and Kynoar (PVDF) with mass ratio 8:1:1's
Ratio joins in N-Methyl pyrrolidone solvent, 10 hours prepared slurries of ball milling, then gained slurry is uniformly coated to 8 micro-
In the thin titanium sheet that rice is thick, lower 120 DEG C of vacuum condition dries 10 hours, finally presses 5 minutes with tablet machine with 10MPa, every square centimeter
The quality of active material is about 5mg, obtains being applicable to the negative material (bismuth oxide powder electrode) of Water based metal ion battery.
Test the present embodiment gained negative material chemical property in sodium nitrate solution:
Using above-mentioned bismuth oxide powder electrode as working electrode, with metal platinized platinum for electrode, saturated calomel electrode conduct
Reference electrode, electrolyte is the sodium nitrate solution of 1mol/L, the cycle performance of this negative material and charging and discharging curve such as Fig. 4 institute
Show, wherein A be charging and discharging currents density be 2mA/cm2Under circulation figure, it is known that the capacity of bismuth oxide is 1.45mAh/cm2, pass through
50 circulations, the capability retention of bismuth oxide is 82%；B be electric current density be 6.5mA/cm2Under circulation figure, it is known that bismuth oxide
Capacity be maintained at 0.6mAh/cm2, after 140 circulations, capability retention is 80.5%；C is charging and discharging currents density difference
For 2mA/cm2And 6.5mA/cm2Constant current charge-discharge curve chart, illustrate that bismuth oxide powder electrode charge and discharge platform is good, discharge and recharge
High rate performance is excellent.
Embodiment 3
Preparation is applicable to the negative material of Water based metal ion battery: by the five water bismuth nitrate of 0.6g, 6mL ethylene glycol, 6mL
Cleaned titanium sheet is put in bismuth-containing precursor liquid as bismuth-containing precursor liquid, is placed in 20mL polytetrafluoro by acetone stirring for 30 minutes
Ethylene inner bag, then loads inner bag hydrothermal reaction kettle and seals, 120 DEG C of Water Under thermal responses 8 hours, stops heating subsequently
It is cooled to room temperature, by ethanol and deionized water rinsing sample surfaces residual solution, grows one layer of oxidation at titanium sheet collection liquid surface
Bismuth thin film, is i.e. applicable to the negative material of Water based metal ion battery.The scanning electron of negative material surface oxidation bismuth thin film shows
Micro mirror image shows, gained nano bismuth oxide array film pattern is similar to embodiment 1 gained nano bismuth oxide array film.
Embodiment 4
The assembling of the aquo-lithium ion battery of negative material based on embodiment 1 preparation and LiMn2O4 electrode and electrochemistry
Can test.
The preparation of LiMn2O4 electrode: LiMn2O4 powder, white carbon black and PVDF are joined N-methylpyrrole with the ratio of 8:1:1
In alkanone solvent, 10 hours prepared slurries of ball milling, by thin titanium sheet thick for slurry uniform application to 8 micron, under vacuum condition 120
DEG C dry 10 hours, finally with tablet machine with 10MPa pressure within 5 minutes, obtain LiMn2O4 electrode.
With the negative material prepared by embodiment 1 as negative pole, above-mentioned LiMn2O4 electrode is positive pole, cuts collocation according to specification
Being assembled into battery, the barrier film used is commercially available nickel-hydrogen battery separator, and electrolyte is for mixing lithium ion solution (by lithium sulfate and chlorine
Changing lithium solution to mix with the volume ratio of 1:2, holding lithium concentration is 1mol/L), this battery charging and discharging curve as it is shown in figure 5,
At the operation interval of 0-2.2V, charging and discharging currents is 172mA/g, and the discharge capacity of full battery is 78.9mAh/g, and discharge platform is
About 1V.Under the electric current density that charging and discharging currents is 250mAh/g, circulating the capability retention of battery after 50 times is 60%.
Embodiment 5
The assembling of the aquo-lithium ion battery of bismuth oxide powder electrode based on embodiment 2 preparation and LiMn2O4 electrode and electricity
Chemical property is tested.
With embodiment 2 preparation bismuth oxide powder electrode as negative pole, embodiment 4 preparation LiMn2O4 electrode be positive pole, press
Cutting collocation according to specification and be assembled into battery, the barrier film used is commercially available nickel-hydrogen battery separator, and electrolyte is molten for mixing lithium ion
Lithium sulfate and lithium chloride solution (are mixed, holding lithium concentration is 1mol/L) by liquid with the volume ratio of 1:2, and battery is at different electricity
As shown in Figure 6, at the operation interval of 0-2.2V, charging and discharging currents increases 2,5,10 from 0.025A/g to discharge curve under current density
During with 50 times, the capacity of battery is respectively under the conditions of 0.025A/g the 90% of capacity, 74.7%, 66.1% and 35.75%, works as electricity
Current density increases 100 times, and when 0.025A/g increases to 2.5A/g, capability retention is 26.7%, and the discharge capacity of battery is
78.9mAh/g, under the electric current density that charging and discharging currents is 250mAh/g, after circulating 100 times, capability retention is 68.3%.
Obviously, above-described embodiment is only used to clearly demonstrate the example that the present invention is made, and not real to the present invention
The restriction that the mode of executing is done.For those of ordinary skill in the field, can also make on the basis of the above description
The change of other multi-form or variation.Here without also cannot all of embodiment be given exhaustive.And therefore amplified
Obvious change or variation still in the protection domain of the invention within.
Claims (10)
1. the negative material being applicable to Water based metal ion battery, it is characterised in that: described negative material contains bismuth oxide.
The negative material being applicable to Water based metal ion battery the most according to claim 1, it is characterised in that: described negative pole
Material is nano bismuth oxide array film, and it is made up of oriented growth bismuth oxide nanometer sheet in metallic substrates, and described bismuth oxide is received
Rice sheet Vertical Uniform dense distribution is on the metallic substrate, in array-like.
The negative material being applicable to Water based metal ion battery the most according to claim 2, it is characterised in that described nanometer
The preparation method of bismuth oxide array film is: the titanium sheet of clean surface is placed in and prepares as mixed solvent using ethylene glycol and acetone
In the bismuth-containing precursor liquid obtained, prepare the negative material being applicable to Water based metal ion battery through hydro-thermal reaction.
The negative material being applicable to Water based metal ion battery the most according to claim 1, it is characterised in that: described negative pole
Material mixed homogeneously with conductive additive, binding agent by bismuth oxide powder after on the metallic substrate masking obtain.
The negative material being applicable to Water based metal ion battery the most according to claim 4, it is characterised in that negative material
Preparation method step is as follows:
1) bismuth oxide powder is prepared: obtain bismuth-containing precursor liquid, bismuth-containing precursor liquid using ethylene glycol and acetone as mixed solvent preparation
Bismuth oxide powder is obtained through hydro-thermal reaction post processing again；
2) bismuth oxide powder, conductive additive, binding agent being added in solvent, abundant ball milling prepares slurry, is then starched by gained
Material is coated uniformly in titanium sheet, obtains being applicable to the negative pole material of Water based metal ion battery by tablet machine compression process again after drying
Material.
6. according to the negative material being applicable to Water based metal ion battery described in claim 3 or 5, it is characterised in that described second
Glycol and acetone volume ratio are 1:1-2.
7. according to the negative material being applicable to Water based metal ion battery described in claim 3 or 5, it is characterised in that described contain
Bismuth precursor liquid is dissolved in mixed solvent by five water bismuth nitrate and obtaining；Described hydrothermal temperature is 120-180 DEG C, and the response time is
3-8h。
The negative material being applicable to Water based metal ion battery the most according to claim 6, it is characterised in that: described conduction
Additive is white carbon black, Graphene or CNT, and binding agent is Kynoar or politef, and wherein bismuth oxide powder accounts for
The mass ratio of negative material is 60-80%, and it is 5-20% that conductive additive accounts for the mass ratio of negative material, and binding agent accounts for negative pole material
The mass ratio of material is 5-20%.
9. a Water based metal ion battery, the composition of described Water based metal ion battery includes positive pole, negative pole and electrolyte, its
It is characterised by: described negative pole contains the arbitrary described negative material of claim 1-8.
Water based metal ion battery the most according to claim 9, it is characterised in that: described Water based metal ion battery bag
Include aquo-lithium ion battery, water system sodium-ion battery, water system kalium ion battery, water system Magnesium ion battery, water system calcium ion battery,
The mixing water system of the one or more than one in water system strontium ion battery, water system barium ions battery and water system aluminium ion battery from
Sub-battery；
The electrolyte of described Water based metal ion battery be lithium sulfate, lithium chloride, lithium nitrate, sodium sulfate, sodium chloride, sodium nitrate,
Potassium sulfate, potassium chloride, potassium nitrate, magnesium chloride, magnesium nitrate, calcium chloride, calcium nitrate, strontium chloride, strontium nitrate, barium chloride, barium nitrate,
One or more aqueous solution in aluminum nitrate, pH value of water solution is 2.0-8.0, and cation concn is 0.5-10mol/L.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082453A (en) * | 2017-03-24 | 2017-08-22 | 哈尔滨工程大学 | Preparation and application process as the hydrated iron barium oxide of water system Magnesium ion battery negative material |
| CN108539169A (en) * | 2018-04-16 | 2018-09-14 | 西北工业大学 | A kind of self-assembled structures Bi2O3Zinc-base battery anode material and preparation method |
| WO2018170925A1 (en) * | 2017-03-24 | 2018-09-27 | 深圳先进技术研究院 | Calcium ion secondary cell, and manufacturing method thereof |
| CN109686936A (en) * | 2018-12-17 | 2019-04-26 | 深圳先进技术研究院 | Calcium ion battery cathode active material, negative electrode material, calcium ion battery cathode, calcium ion battery and its preparation method and application |
| CN110474111A (en) * | 2019-06-20 | 2019-11-19 | 宋君 | 3.5V aquo-lithium ion battery |
| CN111799452A (en) * | 2020-06-29 | 2020-10-20 | 安徽师范大学 | Ultrathin porous bismuth oxide nanosheet loaded graphene composite material and preparation method thereof, lithium ion battery cathode and battery |
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| CN114551828A (en) * | 2022-01-28 | 2022-05-27 | 同济大学 | Bi-MOF derived bismuth oxide-based negative electrode material and preparation and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55119355A (en) * | 1979-03-07 | 1980-09-13 | Sanyo Electric Co Ltd | Non-aqueous electrolyte battery |
| CN103053050A (en) * | 2010-08-31 | 2013-04-17 | 丰田自动车株式会社 | Negative electrode material, lithium secondary battery, and method for producing negative electrode material |
| CN104779394A (en) * | 2015-04-17 | 2015-07-15 | 复旦大学 | Aqueous lithium (sodium) ion battery mixed negative material |
| CN105591104A (en) * | 2016-01-21 | 2016-05-18 | 河南师范大学 | Lithium iron phosphate electrode for alkaline secondary cell cathode and preparation method of lithium iron phosphate electrode |
-
2016
- 2016-08-04 CN CN201610632608.5A patent/CN106229498B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55119355A (en) * | 1979-03-07 | 1980-09-13 | Sanyo Electric Co Ltd | Non-aqueous electrolyte battery |
| CN103053050A (en) * | 2010-08-31 | 2013-04-17 | 丰田自动车株式会社 | Negative electrode material, lithium secondary battery, and method for producing negative electrode material |
| CN104779394A (en) * | 2015-04-17 | 2015-07-15 | 复旦大学 | Aqueous lithium (sodium) ion battery mixed negative material |
| CN105591104A (en) * | 2016-01-21 | 2016-05-18 | 河南师范大学 | Lithium iron phosphate electrode for alkaline secondary cell cathode and preparation method of lithium iron phosphate electrode |
Non-Patent Citations (1)
| Title |
|---|
| WENHUA ZUO ET AL.: ""Direct Growth of Bismuth film as anode for aqueous rechargeable battries in LiOH,NaOH AND KOH Electrolytes"", 《NANOMATERIALS》 * |
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