CN106409532B - A kind of method that electrochemistry alkali activation method prepares the embedded supercapacitor of polyion - Google Patents

A kind of method that electrochemistry alkali activation method prepares the embedded supercapacitor of polyion Download PDF

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CN106409532B
CN106409532B CN201610922150.7A CN201610922150A CN106409532B CN 106409532 B CN106409532 B CN 106409532B CN 201610922150 A CN201610922150 A CN 201610922150A CN 106409532 B CN106409532 B CN 106409532B
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ldh
supercapacitor
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CN106409532A (en
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邵明飞
栗振华
卫敏
段雪
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Beijing University of Chemical Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
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  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses a kind of methods that electrochemistry alkali activation method prepares the embedded supercapacitor of polyion.The transition metal hydroxide containing cobalt or nickel is activated or is deactivated processing using simple and quick electrochemistry alkali activation method, realize that the hydroxide species electrode material to the intelligent control of various metals cation storage capacity, is applied to the embedded supercapacitor of ion.The present invention provides a kind of more pervasive methods that can be improved the embedded electrode material for super capacitor energy-storage property of ion, and have further widened transition metal hydroxide class electrode material in the application range of energy storage field.

Description

A kind of method that electrochemistry alkali activation method prepares the embedded supercapacitor of polyion
Technical field
The invention belongs to inorganic nano materials to synthesize field, in particular to it is embedding that a kind of electrochemistry alkali activation method prepares polyion Enter the more pervasive method of formula supercapacitor.
Background technique
With the continuous improvement of science and technology being constantly progressive with human living standard, demand of the people for material life It has been not limited solely to solve the basic living problems, but has pursued more convenient, highly efficient, more colorful life.Nowadays Panoramic power driven equipment is being enriched constantly the visual field of people, however these equipment, arrives electric crane, electronic greatly Automobile, small to mobile, laptop, mp3 etc. are faced with identical problem invariably, that is, need highly efficient energy storage and confession It can equipment.Along with the extensive use of the development of battery technology in recent years, especially lithium ion battery, the capacity of battery is increasingly Height, it is also increasingly longer that electronic product fills the time that primary electricity can continue a journey.But in electric car, home electric, space flight facility Deng the electronics field for needing larger immediate current, conventional batteries face bottleneck since power density is low in use.In This simultaneously, although traditional capacitor charge-discharge velocity is fast, has extended cycle life, there is also shortcomings.For example capacity density is too It is low, self-discharge phenomenon is serious, operating voltage is low etc., these all greatly limit the practicality.Therefore seek that there is high ratio simultaneously Capacity and high-specific-power, having extended cycle life etc. has excellent performance and cheap, clean new energy device, is that the energy is led in world wide One of most concerned project of the scientists in domain.
In order to enable energy storage device to possess high power density and energy density and good stable circulation simultaneously Property, scientific research personnel proposes the concept of supercapacitor.It combines the advantages of conventional batteries and traditional capacitor, when having charging Between short, long service life, good temp characteristic, it is energy saving and environmentally protective the features such as, be expected to become a kind of emerging high-efficiency energy-storage Device.Supercapacitor can be divided into double layer capacitor and pseudocapacitors from energy storage mechnism.The supercapacitor studied at present Electrode material is concentrated mainly on carbon material, conducting polymer and inorganic, metal oxide/hydroxide etc..Although super capacitor Device has the advantages that many tempting, but it further development and practical is still faced with huge challenge.This is concentrated mainly on: One, electrode material is difficult to meet high-energy density simultaneously in practical applications, the need of the service life of fast charging and discharging and length It asks.Although being regulated and controled by Material cladding or micro-nano structure, people super capacitor material research field achieve it is certain into Exhibition, but seek efficient, low-cost super capacitor electrode material and still suffer from challenge;Two, super based on alkaline electrolyte Capacitor is still faced with the low disadvantage of energy storage potential window, these all restrict the practicalization of supercapacitor.
In order to solve these problems, it is super to propose ion embedded type on the basis of original supercapacitor by scientific research personnel The concept of grade capacitor.It is different from double layer capacitor and fake capacitance capacitor, relies primarily on metal cation in electrode material Surface or internal quick intercalation/deintercalation are expected to store and discharge charge.In this course, since metal cation is embedding Redox reaction does not occur with electrode material when entering/deviating from, therefore it possesses more relative to conventional metals ion battery More quick charge and discharge can be realized in high power density.In addition electrolyte master used in ion embedded type supercapacitor If neutral metal salt electrolyte, therefore it possesses higher energy storage potential window relative to traditional supercapacitor.At present Metal carbides (MC is concentrated mainly on for the research of ion embedded type electrode material for super capacitorX), metal sulfide (MSX) and metal oxide (MOX) on, wherein MXene is as a kind of novel laminated metal carbide with satisfactory electrical conductivity, The continuous concern that attract scientific research personnel has become the main force for leading ion embedded type electrode material for super capacitor to develop Army.Although scientific research personnel for ion embedded type electrode material for super capacitor research on have been achieved for it is very big into Step, but also faces problems on the whole, such as: one, the ability of electrode material storage metal ion is low, poorly conductive, system Standby at high cost etc., these require further to develop the Novel electric for possessing more preferable performance for being suitble to the quick intercalation/deintercalation of cation Pole material;Two, most of electrode material is just for Li+With preferable intercalation/deintercalation performance, and for other metal cations (Na+、K+、Ca2+、Mg2+、Zn2+、Al3+) do not have storage performance or poor performance.But consider from earth's crust content, Li+On ground Content in shell is opposite minimum with other metal cations, therefore exploitation is suitble to the electrode of other metal cation intercalation/deintercalations Material is extremely urgent.
Summary of the invention
The present invention for current ion insertion-host electrode materials storage metal ion ability is low, poorly conductive, preparation Deficiency at high cost etc. is proposed with metal hydroxides (MOHX) it is used as novel ion embedded type electrode of super capacitor material Material, the metal ion storage performance of electrode material is improved by simple electrochemistry alkali activation method.It is of the invention based on letter Single quickly electrochemistry alkali activation method prepare the embedded supercapacitor of polyion specific steps are as follows:
1) for using the metal hydroxides nano material containing cobalt or nickel as anode, 20-50mL concentration are the alkalinity of 1-5g/L Solution is as electrolyte, by cyclic voltammetry, in 1-100mV s-1Sweep speed under, in 0-0.1V to the current potential of 0-0.8V Under window, scan round 1-50 time, it is activated;
2) using step 1) by the metal hydroxides nano material containing cobalt or nickel that is activated as positive, 20- 50mL concentration is the alkaline solution of 1-5g/L as electrolyte, by cyclic voltammetry, in 1-100mV s-1Sweep speed under, Under the potential window of 0-(- 0.1V) to 0-(- 1.5V), scan round 1-50 time, processing of deactivating is carried out;
3) deactivates the metal hydroxides containing cobalt or nickel by being activated of step 1) or the process of step 2) Processing is used as anode containing the metal hydroxides of cobalt or nickel, more with nitrate or sulfate the electrolyte solution composition of 1-5g/L The embedded supercapacitor of ion carries out ion storage performance test.
Step 1) or 2) described in the alkaline solution as electrolyte are as follows: one or more of KOH, NaOH, LiOH.
Contain cobalt hydroxide used in step 1) are as follows: Co (OH)2、CoNi-LDH、CoFe-LDH、CoAl-LDH、CoMn- One or more of LDH, CoV-LDH.
Contain nickel hydroxide used in step 1) are as follows: Ni (OH)2、NiFe-LDH、NiAl-LDH、NiMn-LDH、NiV- One or more of LDH.
Metal nitrate salt electrolyte used in step 3) are as follows: LiNO3、NaNO3、KNO3、Ca(NO3)2、Mg(NO3)2Or Zn (NO3)2
Metal sulfate salt electrolyte used in step 3) are as follows: Li2SO4、Na2SO4、K2SO4、CaSO4、MgSO4Or ZnSO4
The present invention has the advantages that by a kind of simple and quick electrochemistry alkali activation method to the hydroxide containing cobalt or nickel Activated or deactivated processing, realizes such hydroxide electrode material to the intelligence of various metals cation storage capacity Regulation, can be efficiently applied to the embedded supercapacitor of ion;Provide that a kind of completely new can to increase substantially ion embedding Enter the more pervasive method of formula electrode material for super capacitor energy-storage property;Transition metal hydroxide class is further widened Application range of the electrode material in energy storage field.
Detailed description of the invention
Fig. 1 is that the metal hydroxides electrochemistry alkali in embodiment 1 activates and deactivates and metal cation insertion is de- Mechanism figure out.
Fig. 2 is the ferro-cobalt hydrotalcite for being activated front and back (being indicated respectively with AA and BA) in embodiment 1 by electrochemistry alkali To the cyclic voltammetry curve of different metal cation storage.
Fig. 3 is the ferro-cobalt hydrotalcite for being activated front and back (being indicated respectively with AA and BA) in embodiment 1 by electrochemistry alkali To the charging and discharging curve of different metal cation storage.
Fig. 4 is in embodiment 1 by electrochemistry alkali activation (being indicated with AA) and treated the cobalt of deactivating and (indicated with DA) Intelligent control cyclic voltammetry curve of the molten iron talcum to lithium ion storage capacity.
Fig. 5 is that the ferro-cobalt hydrotalcite in embodiment 1 after electrochemistry alkali activation processing passes through continuous 10000 charge and discharges Stability curve after electrical testing.
Specific embodiment
Embodiment 1
1) is activated ferro-cobalt hydrotalcite:
A: preparing 50ml concentration is the KOH solution of 5g/L as electrolyte;
B: using ferro-cobalt hydrotalcite nano array as anode, by cyclic voltammetry, in 100mV s-1Sweep speed under, Under the potential window of 0-0.6V, scan round 5 times, it is activated;
2) carries out processing of deactivating to ferro-cobalt hydrotalcite:
A: preparing 50ml concentration is the KOH solution of 5g/L as electrolyte;
B: using step 1) by the ferro-cobalt hydrotalcite nano array that is activated as positive, by cyclic voltammetry, In 100mV s-1Sweep speed under, under the potential window of 0-(- 0.6V), scan round 5 times, carry out processing of deactivating;
3) neutral electrolyte solution electrochemistry energy-storage property is probed into
Using step 1) or 2) by activation processing or the ferro-cobalt hydrotalcite for processing of deactivating as anode, respectively in 5g/L Nitrate (LiNO3、NaNO3、KNO3、Ca(NO3)2、Mg(NO3)2、Zn(NO3)2) or sulfate (Li2SO4、Na2SO4、K2SO4、 CaSO4、MgSO4、ZnSO4) ion storage performance test is carried out in electrolyte solution.
Embodiment 2
1) is activated cobalt aluminum hydrotalcite:
A: preparing 50ml concentration is the NaOH solution of 4g/L as electrolyte;
B: using cobalt aluminum hydrotalcite nano array as anode, by cyclic voltammetry, in 100mV s-1Sweep speed under, Under the potential window of 0-0.5V, scan round 10 times, it is activated;
2) carries out processing of deactivating to ferro-cobalt hydrotalcite:
A: preparing 50ml concentration is the NaOH solution of 4g/L as electrolyte;
B: using step 1) by the ferro-cobalt hydrotalcite nano array that is activated as positive, by cyclic voltammetry, In 50mV s-1Sweep speed under, under the potential window of 0-(- 0.5V), scan round 10 times, carry out processing of deactivating;
3) neutral electrolyte solution electrochemistry energy-storage property is probed into
Using step 1) or 2) by activation processing or the cobalt aluminum hydrotalcite for processing of deactivating as anode, respectively in 5g/L Nitrate (LiNO3、NaNO3、KNO3、Ca(NO3)2、Mg(NO3)2、Zn(NO3)2) or sulfate (Li2SO4、Na2SO4、K2SO4、 CaSO4、MgSO4、ZnSO4) ion storage performance test is carried out in electrolyte solution.
Embodiment 3
1) is activated cobalt hydroxide:
A: preparing 50ml concentration is the LiOH solution of 6g/L as electrolyte;
B: using cobalt hydroxide nano-array as anode, by cyclic voltammetry, in 100mV s-1Sweep speed under, 0- Under the potential window of 0.1V, scan round 20 times, it is activated;
2) carries out processing of deactivating to cobalt hydroxide:
A: preparing 50ml concentration is the LiOH solution of 6g/L as electrolyte;
B: using step 1) by the cobalt hydroxide nano-array that is activated as positive, by cyclic voltammetry, 100mV s-1Sweep speed under, under the potential window of 0-(- 0.1V), scan round 10 times, carry out processing of deactivating;
3) neutral electrolyte solution electrochemistry energy-storage property is probed into
Using step 1) or 2) by activation processing or the cobalt hydroxide for processing of deactivating as anode, respectively 5g/L's Nitrate (LiNO3、NaNO3、KNO3、Ca(NO3)2、Mg(NO3)2、Zn(NO3)2) or sulfate (Li2SO4、Na2SO4、K2SO4、 CaSO4、MgSO4、ZnSO4) ion storage performance test is carried out in electrolyte solution.
Embodiment 4
1) is activated nickel hydroxide:
A: preparing 50ml concentration is the KOH solution of 5g/L as electrolyte;
B: using nickel hydroxide nano array as anode, by cyclic voltammetry, in 1-100mV s-1Sweep speed under, Under the potential window of 0-0.1V, scan round 5 times, it is activated;
2) carries out processing of deactivating to nickel hydroxide:
A: preparing 50ml concentration is the KOH solution of 5g/L as electrolyte;
B: using step 1) by the nickel hydroxide nano array that is activated as positive, by cyclic voltammetry, 100mV s-1Sweep speed under, under the potential window of 0-(- 0.1V), scan round 5 times, carry out processing of deactivating;
3) neutral electrolyte solution electrochemistry energy-storage property is probed into
Using step 1) or 2) by activation processing or the nickel hydroxide for processing of deactivating as anode, respectively 5g/L's Nitrate (LiNO3、NaNO3、KNO3、Ca(NO3)2、Mg(NO3)2、Zn(NO3)2) or sulfate (Li2SO4、Na2SO4、K2SO4、 CaSO4、MgSO4、ZnSO4) ion storage performance test is carried out in electrolyte solution.

Claims (6)

1. a kind of method that electrochemistry alkali activation method prepares the embedded supercapacitor of polyion, which is characterized in that concrete operations Steps are as follows:
1) for using the metal hydroxides nano material containing cobalt or nickel as anode, 20-50 mL concentration is the alkalinity of 1-5 g/L Solution is as electrolyte, by cyclic voltammetry, in 1-100 mV s-1Sweep speed under, in the electricity of 0-0.1V to 0-0.8V Under the window of position, scan round 1-50 times is activated;
2) metal hydroxides nano material containing cobalt or nickel of the using step 1) by activation processing is as anode, 20-50 mL Concentration is the alkaline solution of 1-5 g/L as electrolyte, by cyclic voltammetry, in 1-100 mV s-1Sweep speed under, 0-(-0.1V) under the potential window of 0-(-1.5V), scan round 1-50 times carries out processing of deactivating;
3) deactivates the metal hydroxides containing cobalt or nickel by being activated of step 1) or the process of step 2) Nitrate or sulfate the electrolyte solution composition containing the metal hydroxides of cobalt or nickel as anode, with 1-5 g/L of processing The embedded supercapacitor of polyion carries out ion storage performance test.
2. according to the method described in claim 1, it is characterized in that step 1) or 2) described in the alkalinity as electrolyte Solution are as follows: one or more of KOH, NaOH, LiOH.
3. according to the method described in claim 1, it is characterized in that containing cobalt hydroxide used in step 1) are as follows: Co (OH)2、 One or more of CoNi-LDH, CoFe-LDH, CoAl-LDH, CoMn-LDH, CoV-LDH.
4. according to the method described in claim 1, it is characterized in that containing nickel hydroxide used in step 1) are as follows: Ni (OH)2、 One or more of NiFe-LDH, NiAl-LDH, NiMn-LDH, NiV-LDH.
5. the preparation method of electrode material according to claim 1, it is characterised in that nitrate used in step 3) Are as follows: LiNO3、NaNO3、KNO3、Ca(NO3)2、Mg(NO3)2Or Zn (NO3)2
6. the preparation method of electrode material according to claim 1, it is characterised in that sulfate used in step 3) Are as follows: Li2SO4、Na2SO4、K2SO4、CaSO4、MgSO4Or ZnSO4
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CN107369566A (en) * 2017-07-27 2017-11-21 桂林理工大学 A kind of preparation method and application of ultracapacitor cobalt nickel hydrotalcite electrode material
CN110346437B (en) * 2019-07-15 2022-03-15 北京工商大学 LDHs/MXene-based electrochemical glucose sensor and preparation and application thereof
CN111029172A (en) * 2019-12-31 2020-04-17 青岛科技大学 Two-dimensional layered supercapacitor electrode material Ti3C2Interlayer structure regulation and control method of MXene
CN111575730B (en) * 2020-04-27 2022-08-19 大连理工大学 Preparation method of integral carbon-based electrode for seawater electrolysis
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CN113512737B (en) * 2021-04-01 2022-07-19 安徽大学 Nickel hydroxide electrocatalyst, preparation method, electrochemical activation method and application thereof
CN113279009B (en) * 2021-04-28 2022-05-27 北京化工大学 Preparation method of composite photo-anode with hole-transport and cocatalyst double-function photoelectrocatalysis interface
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