CN109786677A - A kind of zinc-nickel single flow battery positive electrode and preparation and application - Google Patents
A kind of zinc-nickel single flow battery positive electrode and preparation and application Download PDFInfo
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- CN109786677A CN109786677A CN201711106271.5A CN201711106271A CN109786677A CN 109786677 A CN109786677 A CN 109786677A CN 201711106271 A CN201711106271 A CN 201711106271A CN 109786677 A CN109786677 A CN 109786677A
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Abstract
The present invention relates to a kind of zinc-nickel single flow battery positive electrodes and preparation and application, the positive electrode to be made of nickel oxide particle and metal sulfide, and metal sulfide is coated on nickel oxide particle surface；The metal sulfide is the sulfide of one of Zn, Fe, Cd, Pb, Cu or Ag or two kinds or more.Present invention firstly provides nickel sulfides, and cobalt oxide to be replaced to be coated on nickel oxide surfaces as Zn-Ni liquid battery anode.Solve current material poor circulation, the higher problem of covering material price.
Description
Technical field
The present invention relates to Zn-Ni liquid battery electrode material field, specially a kind of zinc-nickel single flow battery positive electrode
And it prepares and applies.
Background technique
Zn-Ni liquid battery is the novel low cost of one kind, high efficiency, environmentally friendly flow battery, has energy close
Degree and current efficiency is high, the simple steerable, long service life of device, it is low in cost the advantages that, be mainly used in peak load regulation network, wind
The fields such as renewable energy power generations, the electric car such as energy and solar energy.
Zn-Ni liquid battery electrolyte is the zincate alkaline solution of flowing, does not use amberplex in battery, passes through
The free-flowing of ion and the directed movement of external circuit electronics constitute current loop in battery cavities.
But due to the low conductivity feature and volume expansion problem of nickel oxide, cause its stability poor, it is logical at present
It is often to coat cobalt oxide in nickel oxide surfaces, forms composite material, to limit the volume expansion in cyclic process, improves conductive
Property.
However, the price of cobalt is higher, it is difficult to meet large-scale application.And nickel oxide is easy to happen crystal form at high temperature and turns
Become, it is difficult to carry out charcoal cladding.
Summary of the invention
The Zn-Ni liquid battery uniformly coated by metal sulfide it is an object of that present invention to provide a kind of nickel oxide surfaces is just
Pole material and preparation method.
The purpose of the invention is achieved by the following technical solution:
A kind of zinc-nickel single flow battery positive electrode, the positive electrode is by nickel oxide particle and metal sulfide structure
At metal sulfide is coated on nickel oxide particle surface；The metal sulfide is one of Zn, Fe, Cd, Pb, Cu or Ag
Or two kinds or more of sulfide.
Nickel oxide mass percentage 60%-90% in positive electrode, nickel oxide particle partial size is in 100nm-1um.
Including following preparation step,
It is dissolved to be formed with hydro-thermal complex reaction after nickel oxide particle, water-soluble metal sulfide and organic additive are mixed
The solution for the metal ion that molar concentration is 0.05-1mol/L is added in solution or colloidal sol, ultrasonic disperse, naturally cold after reaction
But, it washed, filtered respectively with organic solvent and deionized water, be dried to obtain the nickel oxyhydroxide material of metal sulfide cladding.
The water-soluble metal sulfide is one of vulcanized sodium, potassium sulfide, cesium sulfide or two kinds or more；
The organic additive is N- polyvinylpyrrolidone (PVP), cetrimonium bronmide (CTAB), poly- second two
One of alcohol, Nafion or dodecyl sodium sulfate (SDS) or two kinds or more；
Water-soluble metal sulfide concentration is 0.05-1mol/L in hydro-thermal complex reaction system；
The concentration of organic additive is 0.01-1mol/L in hydro-thermal complex reaction system；
The mass concentration of nickel oxide particle is 2-5g/L in hydro-thermal complex reaction system；
The temperature of the hydro-thermal complex reaction is 20-60 DEG C, reaction time 2-30h, and reaction pH is 3~12.
The time of the ultrasonic disperse is 0.5-3h；
The anion of the metal ion solution is acetate, nitrate anion, Cl-One of or two kinds or more；Metal
For one of Zn, Fe, Cd, Pb, Cu or Ag or two kinds or more.
Organic solvent used in the washing process is dehydrated alcohol, acetone, butanol or carbon tetrachloride.
Application of the positive electrode in Zn-Ni liquid battery.
The preparation method of Zn-Ni liquid battery positive electrode of the present invention includes the following steps:
The preparation principle of metal sulfide cladding nickel oxyhydroxide material of the present invention are as follows:
Nickel oxide, water-soluble metal sulfide and organic additive are formed into solution or sol form mixes, is added using organic
Add agent to be enriched in nickel oxide surfaces, and the sulphion in adsorbent solution, is added after containing Zn, Fe, Cd, Pb, Cu, Ag ion in low temperature
Lower progress hydro-thermal complex reaction, due to nickel oxide under this condition under be still dispersed in solution with solid granulates, can
Nickel oxide is carried out sulfide cladding.Since sulphion is added agent uniform adsorption on sulphur simple substance surface, be easy by Zn, Fe,
Cd, Pb, Cu, Ag ion complexation form metal sulfide and cover positive electrode particle surface, and material surface is evenly distributed, in conjunction with tight
It is close.By adjusting reactant ratio in experimentation, best product is can be obtained in reaction time, temperature, pH value.
Beneficial effects of the present invention:
Since metal sulfide itself has semiconductor property, certain electron electric conductivity can be provided；Metal vulcanization
Object has good proton transport ability, ensure that the proton transport under close capsulation condition；Metal sulfide is in nickel oxide table
The cladding in face can be realized in mild chemical environment, simple and easy.
Traditional Zn-Ni liquid battery just extremely nickel oxide.But due to the low conductivity feature and volume of nickel oxide
Expansion issues cause its stability poor, and current common solution is to coat cobalt oxide in nickel oxide surfaces, are formed compound
Material improves electric conductivity to limit the volume expansion in cyclic process.However, the price of cobalt is higher, it is difficult to which satisfaction is answered on a large scale
With.Present invention firstly provides nickel sulfides, and cobalt oxide to be replaced to be coated on nickel oxide surfaces as Zn-Ni liquid battery anode.It solves existing
There is material circulation performance poor, the higher problem of covering material price.
Detailed description of the invention
Fig. 1 is 1 Zn-Ni liquid battery of embodiment in 40mA/cm2Under the conditions of charge-discharge performance figure；
Fig. 2 is positive electrode SEM figure prepared by embodiment 1；
Fig. 3 is 2 Zn-Ni liquid battery of embodiment in 40mA/cm2Under the conditions of charge-discharge performance figure；
Fig. 4 is positive electrode SEM figure prepared by embodiment 2；
Fig. 5 is 3 Zn-Ni liquid battery of embodiment in 40mA/cm2Under the conditions of charge-discharge performance figure；
Fig. 6 is positive electrode SEM figure prepared by embodiment 3；
Fig. 7 is the Zn-Ni liquid battery of comparative example 1 in 40mA/cm2Under the conditions of charge-discharge performance figure；
Fig. 8 is the Zn-Ni liquid battery of comparative example 2 in 40mA/cm2Under the conditions of charge-discharge performance figure.
Specific embodiment
It is explained further the present invention with reference to embodiments, but embodiment does not do any type of limit to the present invention
It is fixed.
Embodiment 1
By 0.05mol nickel oxide, 0.05mol Na2S, 0.01mol PVP is put into 50ml deionized water, ultrasonic disperse
2h, control pH value are 7, are slowly added to 0.05mol copper acetate later, react 10h at 30 DEG C.To reactant natural cooling, second is used
Alcohol replaces washing 3 times with deionized water, filters, then freeze-day with constant temperature for 24 hours, both obtains target product, as positive electrode at 50 DEG C
Zn-Ni liquid battery is assembled, cathode is zinc metal sheet, and electrolyte is the 6M potassium hydroxide solution of 0.4M zinc ion.Battery is in 40mA/cm2
Under the conditions of, charging time 1h, charge-discharge performance is shown in Fig. 1, and energy efficiency remains at 80% or more after battery 35 times circulations.
Embodiment 2
By 0.05mol nickel oxide, 0.05mol/LNa2S, 0.05mol Nafion is put into 50ml deionized water, ultrasound point
2h is dissipated, control pH value is 5, and 0.1mol nickel nitrate is added later, and mixture is moved into autoclave and is sealed, is reacted at 60 DEG C
10h.To reactant natural cooling, replace with deionized water washing 3 times with ethyl alcohol, filter, then at 50 DEG C freeze-day with constant temperature for 24 hours,
Both target product is obtained.Battery 40mA/cm2Under the conditions of charge-discharge performance see Fig. 3, energy efficiency is still after battery 100 times circulations
It is maintained at 80% or more.
Embodiment 3
By 0.05mol nickel oxide, 0.05mol/LNa2S, 0.05mol SDS is put into 50ml deionized water, ultrasonic disperse
2h, control pH value are 10, and 0.05mol nickel nitrate and 0.05mol copper chloride are added later, and mixture is moved into autoclave simultaneously
It seals, reacts 10h at 60 DEG C.To reactant natural cooling, replace washing 3 times with deionized water with ethyl alcohol, filters, then at 50 DEG C
Lower freeze-day with constant temperature for 24 hours, both obtains target product.Battery 40mA/cm2Under the conditions of charge-discharge performance see Fig. 5, follow for battery 170 times
Energy efficiency remains at 80% or so after ring.
Comparative example 1: nickel oxide assembles Zn-Ni liquid battery as positive electrode, and cathode is zinc metal sheet, and electrolyte is 0.4M zinc
The 6M potassium hydroxide solution of ion.Battery is in 40mA/cm2Under the conditions of, charging time 1h, charge-discharge performance is shown in Fig. 7, battery
Energy efficiency is only 70% or so.
Comparative example 2: nickel oxide surfaces coat cobalt oxide as positive electrode and assemble Zn-Ni liquid battery, and cathode is zinc metal sheet,
Electrolyte is the 6M potassium hydroxide solution of 0.4M zinc ion.Battery is in 40mA/cm2Under the conditions of, charging time 1h, charge and discharge cycles
Performance is shown in Fig. 8, and energy content of battery efficiency is only 77% or so.
Claims (7)
1. a kind of zinc-nickel single flow battery positive electrode, it is characterised in that: the positive electrode is by nickel oxide particle and metal
Sulfide is constituted, and metal sulfide is coated on nickel oxide particle surface；The metal sulfide is Zn, Fe, Cd, Pb, Cu or Ag
One of or two kinds or more of sulfide.
2. according to positive electrode described in claim 1, it is characterised in that: nickel oxide mass percentage 60%- in positive electrode
90%, nickel oxide particle partial size is in 100nm-1um.
3. a kind of preparation method of any positive electrode of claim 1-2, it is characterised in that: including following preparation step,
Will nickel oxide particle, water-soluble metal sulfide and organic additive mix after with hydro-thermal or precipitation reaction formed solution or
The solution for the metal ion that molar concentration is 0.05-1mol/L, natural cooling after reaction, with having is added in colloidal sol, ultrasonic disperse
Solvent and deionized water are washed respectively, are filtered, and the nickel oxyhydroxide material of metal sulfide cladding is dried to obtain.
4. preparation method according to claim 3, it is characterised in that: the water-soluble metal sulfide is vulcanized sodium, sulphur
Change one of potassium, cesium sulfide or two kinds or more；
The organic additive be N- polyvinylpyrrolidone (PVP), cetrimonium bronmide (CTAB), polyethylene glycol,
One of Nafion or dodecyl sodium sulfate (SDS) or two kinds or more；
Water-soluble metal sulfide concentration is 0.05-1mol/L in hydro-thermal complex reaction system；
The concentration of organic additive is 0.01-1mol/L in hydro-thermal complex reaction system；
The mass concentration of nickel oxide particle is 2-5g/L in hydro-thermal complex reaction system；
The temperature of the hydro-thermal complex reaction is 20-60 DEG C, reaction time 2-30h, and reaction pH is 3~12, preferably 5-6.
5. preparation method according to claim 3, it is characterised in that:
The time of the ultrasonic disperse is 0.5-3h；
The anion of the metal ion solution is acetate, nitrate anion, Cl-One of or two kinds or more；Metal be Zn,
One of Fe, Cd, Pb, Cu or Ag or two kinds or more.
6. the preparation method according to claim 4, it is characterised in that: organic solvent used in the washing process is nothing
Water-ethanol, acetone, one of butanol or carbon tetrachloride or two kinds or more.
7. a kind of application of any positive electrode of claim 1-2 in Zn-Ni liquid battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112289982A (en) * | 2019-07-22 | 2021-01-29 | 比亚迪股份有限公司 | Positive electrode material, preparation method thereof and solid-state lithium battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101623645A (en) * | 2009-08-10 | 2010-01-13 | 西安建筑科技大学 | Preparation for p-n junction hollow sphere and application in photocatalytic hydrogen production by water decomposition |
| US20130113431A1 (en) * | 2009-10-14 | 2013-05-09 | Research Foundation Of The City University Of New York | Nickel-Zinc Flow Battery |
| CN103579628A (en) * | 2012-07-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Zinc-nickel single-fluid cell anode, preparation method of zinc-nickel single-fluid cell anode, and zinc-nickel single-fluid cell |
| CN103840187A (en) * | 2012-11-23 | 2014-06-04 | 中国科学院大连化学物理研究所 | Semi-solid-state zinc nickel flow cell |
| CN107200363A (en) * | 2017-05-22 | 2017-09-26 | 安徽建筑大学 | Core shell structure NiO CdS Coaxial Nanofibers and preparation method thereof |
-
2017
- 2017-11-10 CN CN201711106271.5A patent/CN109786677B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101623645A (en) * | 2009-08-10 | 2010-01-13 | 西安建筑科技大学 | Preparation for p-n junction hollow sphere and application in photocatalytic hydrogen production by water decomposition |
| US20130113431A1 (en) * | 2009-10-14 | 2013-05-09 | Research Foundation Of The City University Of New York | Nickel-Zinc Flow Battery |
| CN103579628A (en) * | 2012-07-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Zinc-nickel single-fluid cell anode, preparation method of zinc-nickel single-fluid cell anode, and zinc-nickel single-fluid cell |
| CN103840187A (en) * | 2012-11-23 | 2014-06-04 | 中国科学院大连化学物理研究所 | Semi-solid-state zinc nickel flow cell |
| CN107200363A (en) * | 2017-05-22 | 2017-09-26 | 安徽建筑大学 | Core shell structure NiO CdS Coaxial Nanofibers and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YUANHUI CHENG ET AL.: "Zinc-nickel single flow batteries with improved cycling stability by eliminating zinc accumulation on the negative electrode", 《ELECTROCHIMICA ACTA》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112289982A (en) * | 2019-07-22 | 2021-01-29 | 比亚迪股份有限公司 | Positive electrode material, preparation method thereof and solid-state lithium battery |
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