CN104377374B - One kind is without additional electrolytic cell - Google Patents
One kind is without additional electrolytic cell Download PDFInfo
- Publication number
- CN104377374B CN104377374B CN201410462163.1A CN201410462163A CN104377374B CN 104377374 B CN104377374 B CN 104377374B CN 201410462163 A CN201410462163 A CN 201410462163A CN 104377374 B CN104377374 B CN 104377374B
- Authority
- CN
- China
- Prior art keywords
- electrolytic cell
- battery
- solution
- additional electrolytic
- positive pole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000007769 metal material Substances 0.000 claims abstract description 5
- 229920000767 polyaniline Polymers 0.000 claims description 20
- 239000011777 magnesium Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- 230000005540 biological transmission Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005187 foaming Methods 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 229920002959 polymer blend Polymers 0.000 claims description 3
- 230000008961 swelling Effects 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004425 Makrolon Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 238000005191 phase separation Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000006260 foam Substances 0.000 description 18
- 150000003840 hydrochlorides Chemical class 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of without additional electrolytic cell and its anode preparation method.The battery is formed by positive pole and the compacting of negative pole directly contact：Negative material is a kind of metal material with electro-chemical activity；Positive electrode has electronic conductivity and ionic conductivity difference for a kind of, and has spongy electro-chemical activity polymeric material.The battery is free of incendive electrolyte, and reusable edible, continuous discharge can prepare the battery such as flexible, miniature, ultra-thin, and can be combined with hydrogen fuel cell, so as to the coulomb for increasing substantially electroactive metal negative pole changes efficiency.
Description
Technical field
The present invention relates to field of batteries, it particularly relates to a kind of without additional electrolytic cell and preparation method thereof.
Background technology
Electrochmical power source brings great convenience to human being's production, life, although by optimizing battery structure and electrode material
Material performance can improve the capacity of battery, but its speed for improving does not catch up with the speed of human demand growth increasingly.On the other hand,
The indispensable electrolyte in electrochmical power source inside often triggers all kinds of security incidents.
At present, with the worsening shortages of the fossil fuel resource in global range, people are forced to find new alternative
Clean energy resource.Electrochmical power source turns into preferable alternative energy source due to convenient, cheap, environmentally friendly.From 1990 to
2010, with the invention and the optimization of its electrode material of lithium battery, the energy density rate of rise of commercial cells was from annual 3
Wh/kg is lifted to 5 Wh/kg, even if also can only respectively reach 500 at 2064 and 2100 according to this growth rate
Wh/kg and 700 Wh/kg, far below the actual demand of power-type equipment.On the other hand, if without new battery technology branch
Support, this growth rate at most can only again maintain 20-30.
Electrochmical power source, including one-shot battery, secondary cell, fuel cell and ultracapacitor, all from not in its structure
Addition electrolyte is opened, but just because of the presence of electrolyte, is used to battery and storage is brought great potential safety hazard.I
Only redesign battery basic structure, could fundamentally solve the problems, such as battery low energy and safety.
Metal erosion is a kind of natural phenomena of generally existing, and it is complete by chemical energy in irreversible oxidationreduction mode
Portion dissipates turns into heat energy, and greatly harm is brought to the mankind.However, not all corrosion all has occurrence situation.
Leclanche is prepared for Zn-MnO by accelerating the corrosion of Zn2Dry cell.Due to without a kind of existing cathode material, when it
Both can guarantee that when directly with positive contact it is internal not short-circuit, again can accelerating anode material oxidation-reduction reaction, moreover it is possible to by anode
Oxidation reaction in the electronics released be recycled to negative electrode by external circuit and carry out reduction reaction, so people are typically by reducing gold
Belong to the gas-evolving electrodes of anode to improve its coulomb of conversion efficiency.The normal potential of magnesium is -2.36V (vs SHE), theoretical specific capacity
Up to 2.2Ah/g, is only below lithium (3.86Ah/g), aluminium in common metal（2.98Ah/g）It is small, far above zinc（0.82A.h/
g）；But its price and reserves have very big advantage.At present, magnesium is magnesium as one of the major obstacle of battery anode material
The matching problem of alloy and electrolyte.Under neutral and acid condition, self-corrosion speed is big, makes the reduction of electrode utilization rate；Alkalescence
Under the conditions of, Mg alloy surface can form the diaphragm of densification and make electrode passivation, prevent persistently carrying out for electric discharge.
The content of the invention
The purpose of the present invention be directed to the deficiencies in the prior art and provide a kind of structure without additional electrolytic cell and
Preparation method.The battery is free of incendive electrolyte, and reusable edible, continuous discharge can be prepared flexible, miniature, ultra-thin
Deng battery, and can be combined with hydrogen fuel cell, so as to the coulomb for increasing substantially electroactive metal negative pole changes effect
Rate.
The present invention reaches above-mentioned purpose by the following technical programs.
One kind is formed without additional electrolytic cell, the battery by positive pole and the compacting of negative pole directly contact：
Negative material is a kind of metal material with electro-chemical activity；
Positive electrode has electronic conductivity and ionic conductivity difference for a kind of, and has spongy electro-chemical activity
Polymeric material；
The negative material has oxidation activity, and the positive electrode has electronics and ionic conductivity difference, will be described
Positive pole and negative pole directly contact, form galvanic couple voltage between the two, the water being adsorbed with air is decomposed on the positive electrode and is steamed
Gas, makes the battery last power external circuit.The hydrone for participating in electrochemical reaction is broken down into hydrogen, can be with hydrogen fuel
Battery is combined, and is that it persistently provides the energy.
Specifically, the negative material is one or more in magnesium, zinc, iron, aluminium, calcium or lithium, they are with electricity
Chemically active metal material.
Specifically, the positive electrode is one or more in polyaniline, polythiophene or polypyrrole, they are conduction
High molecular homopolymers or copolymer.
Specifically, the positive electrode prepared by foaming technique, the raw material for preparing the positive electrode is polymethyl
In sour methyl esters, polystyrene, polyethylene, polypropylene, polybutene or makrolon at least two, they are thermoplasticity high score
Sub- material.
Used as a kind of technical scheme, described positive electrode is having added with ionic conductance or the single-phase conductor of electronic conductance
The material of through-hole structure.
The present invention also provides a kind of preparation method without additional electrolytic cell positive pole, comprises the following steps：
S1. co-cable transmission blend is prepared：Polymer is carried out into melt blending；
S2. standard batten is prepared：The particle of the blend is carried out molded；
S3. co-cable transmission sample is prepared：The swelling foaming of standard batten is obtained；
S4. template is prepared：By the co-continuous single-phase extracting of sample, the polymer blend three-dimensional net with through-hole structure is obtained
The template of network；
S5. the positive pole is obtained：Prepare two kinds of solution As, B, solution A：Ammonium persulfate is dissolved in ethanol water, solution
B:Acid solution, aniline and deionized water mixture；Added by described in alkaline solution treatment after solution B is cooled to below 4 DEG C
Template, stirring is slowly added to solution A, reacts 4 ~ 6h, oven drying 24h, removes the template, and freeze-drying obtains porosity
More than 99% co-cable transmission blend positive pole.
An obtained just extremely class porous polymer, while the positive electrode electronic electrical conductivity is weakened, increases it
The ability of ionic conductivity and absorption water, so as to when it is with the negative pole directly contact, can successively decompose it is porous just
The water of extremely internal absorption is simultaneously provided out extrinsic current；The positive pole can effectively overcome metal negative electrode to form short circuit when being in contact with it,
And to external circuit no-voltage and the difficulty of electric current output.The negative metal and the positive pole porous polymer are made described
Without additional electrolytic cell.
Specifically, the method for preparing template uses supercritical CO2Foaming technique, addition chemically or physically foaming agent,
It is separated, orientation is freezed, any one of solvent selectivity dissolving, the template is foamed, and is had by single-phase extracting
There is the template of the polymer blend three-dimensional network of through-hole structure.
The above-mentioned application method without additional electrolytic cell is provided according to demand, and the ambient humidity for using is more than 40%
Or the battery is placed directly in the aqueous solution.
What the present invention was provided will bring following benefit without additional electrolytic cell and preparation method：
1., using safety, capacity is big, nontoxic, adaptable to environmental condition without incendive electrolyte, not only
The electric discharge that can stablize in the condition of humidity 40%, also can the continuous discharge in the aqueous solution, aerobic or oxygen-free environment.
2. reusable edible, it is only necessary to change negative pole, prolonged efficiency can be kept, and replacing options are simple.
3. the battery such as flexible, miniature, ultra-thin can be prepared, and particularly nontoxic minicell can be as micro- in organism
Power supply.
4. byproduct hydrogen gas when being discharged without additional electrolytic cell that the present invention is provided, can be with hydrogen fuel cell
Combination, so as to the coulomb for increasing substantially electroactive metal negative pole changes efficiency.
Brief description of the drawings
Fig. 1 is the schematic diagram without additional electrolytic cell construction；
Fig. 2 is the relation without additional electrolytic cell voltage and time under different discharge current speed；
Fig. 3 is without voltage-time curve of the additional electrolytic cell under 0.1mA constant current discharges（Anode is
Using various concentrations HCl（0.01mol/l, 0.1mol/l and 1mol/l）The polyaniline of doping（PANI）Foam, GND is
Magnesium sheet）；
Fig. 4 is without voltage-time curve of the additional electrolytic cell under 0.1mA constant current discharges（Anode is
Using the different types of acid of 0.1mol/l（HCl, H2SO4And CSA）The PANI foams of doping, GND is magnesium sheet）；
Fig. 5 is in the various concentrations NaOH aqueous solution (0mol/l, 0.01mol/l, 0.1mol/ without additional electrolytic cell
L and 1mol/l) in the voltage-time curve of 0.1mA constant current discharges；
Fig. 6 is discharge time and battery specific energy when circulating to discharge with 0.1mA constant currents without additional electrolytic cell
With the relation of specific capacity；
Fig. 7 is the relation of the open-circuit voltage without additional electrolytic cell and temperature；
Fig. 8 be without additional electrolytic cell under the conditions of 0.05mA, RH=80%, discharge capacity with produce H2Capacity and when
Between curve；
Fig. 9 is without additional electrolytic cell real-time collecting hydrogen device；
Figure 10 is the relation with humidity without additional electrolytic cell open-circuit voltage；
Figure 11 is the relation with oxygen concentration without additional electrolytic cell open-circuit voltage.
Specific embodiment
Embodiment 1
The preparation of polyaniline foam positive pole.By PS, PMMA, MBS（Polybutadienes-polystyrene-polymethyl methacrylate
Triblock copolymer, used as bulking agent）By three-screw extruder（Screw diameter=20 mm, draw ratio=40）Carry out
Melt blending, prepares co-cable transmission blend, and the ratio between three is PS/PMMA/MBS=48/48/4, and rotating speed is 100
Rpm, hopper to each section of temperature of die orifice is respectively 170,180,190,200,210,220 and 210 DEG C.Will blending composition granule note
Molding machine carries out molded（180-240 DEG C of injection temperature, injection pressure 50,40 DEG C of mould temperature）, prepare the standard sample of PMMA/PS
Bar（40×10×4 mm）, this batten is then put into supercritical CO2Swelling 2.5 h of reactor, is let out with the speed of 25 MPa/s
Pressure, swelling condition：The MPa of pressure 25,125 DEG C of temperature, obtains co-cable transmission foamed sample.
Resulting co-cable transmission foamed sample is put into cyclohexane solution carries out single-phase extracting, obtains with through hole knot
The template of the PMMA three-dimensional networks of structure.
Prepare two kinds of solution, solution A：12 mmol ammonium persulfates are dissolved in 250 mL ethanol waters（50%）.It is molten
Liquid B：By 2 mL hydrochloric acid（37%）, 10 mmol aniline and 250 mL deionized waters mixing.After solution B is cooled to below 4 DEG C,
Add through the 3D-PMMA templates of alkali process, after the h of strong agitation 1, solution A is slowly added in solution B, react 4 ~ 6h.Then,
Products obtained therefrom is put into after drying 24h in 60 DEG C of baking ovens, adds dichloromethane to remove the PMMA templates of through hole, be then put into lyophilized
Freeze-drying is carried out in machine, the through hole doped polyaniline foam positive electrode that porosity is more than 99% is obtained.
Embodiment 2
By 10mg with the polyaniline foam of 1mol/l doped hydrochlorides and the Mg paper tinsels of 30mg under the pressure of 2MPa, be made diameter
=1cm, the disk of thickness=1mm, so as to obtain without additional electrolytic cell（See Fig. 1）, then existed with different discharge currents
Same relative humidity（80%）Under carry out test sign（Fig. 2）, wherein specific energy density and specific capacity is entered by the quality of positive pole
Row is calculated.
Embodiment 3
By 10mg with the polyaniline foam of 1mol/l doped hydrochlorides and the Mg paper tinsels of 30mg under the pressure of 2MPa, be made diameter
=1cm, the disk of thickness=1mm, so as to obtain without additional electrolytic cell, then in same discharge current 0.1mA, difference
Test sign is carried out under relative humidity, 1 is the results are shown in Table（Specific energy density and specific capacity in table are carried out by the quality of positive pole
It is calculated）.
Table 1 without quality specific capacitance of the additional electrolytic cell under the conditions of different humidity, 0.05mA discharge rates and
Specific energy
Embodiment 4
First various concentrations HCl is used with 10mg（0.01mol/l, 0.1mol/l and 1mol/l）The polyaniline foam of doping with
The Mg paper tinsels of 30mg are made diameter=1cm, the disk of thickness=1mm, so as to obtain without additional electrolyte under the pressure of 2MPa
, then be placed in this battery in the environment that relative humidity is 80% by battery, is discharged with 0.1mA constant currents, and its result is shown in figure
3。
Embodiment 5
First different acid are used with 10mg（HCl, H2SO4And CSA）Pressure of the polyaniline foam and Mg paper tinsels of doping in 2MPa
Under, it is made diameter=1cm, the disk of thickness=1mm, so as to obtain, without additional electrolytic cell, being then placed in this battery
During relative humidity is 80% environment, discharged under 0.1mA constant currents, its result is shown in Fig. 4.
Embodiment 6
By 10mg with the polyaniline foam of 1mol/l doped hydrochlorides and the Mg paper tinsels of 30mg under the pressure of 2MPa, be made diameter
=1cm, the disk of thickness=1mm, so as to obtain, without additional electrolytic cell, battery then being placed in into various concentrations NaOH water
In solution (0mol/l, 0.01mol/l, 0.1mol/l and 1mol/l), discharged with 0.1mA constant currents, its result is shown in Fig. 5,
Specific energy density and specific capacity are calculated by the quality of positive pole.
Embodiment 7
By 10mg with the polyaniline foam of 1mol/l doped hydrochlorides and the Mg paper tinsels of 30mg under the pressure of 2MPa, be made diameter
=1cm, the disk of thickness=1mm, so as to obtain, without additional electrolytic cell, then battery being placed in the sky of 80% relative humidity
In gas, discharged with 0.1mA constant currents, after having discharged, the polyaniline foam of battery surface is removed, with the hydrochloric acid of 1mol/l
Cleaned, adulterated again, then suppressed with new Mg paper tinsels, prepared without additional electrolytic cell, then tested, schemed
6 is the quality specific capacitance and specific energy of different cycle-indexes.
Embodiment 8
By 10mg with the polyaniline foam of 1mol/l doped hydrochlorides and the Mg paper tinsels of 30mg under the pressure of 2MPa, be made diameter
=1cm, the disk of thickness=1mm, so as to obtain, without additional electrolytic cell, then battery being placed in the ring of 80% relative humidity
In border, the relation of its open-circuit voltage and temperature is tested, its result is shown in Fig. 7.
Embodiment 9
By 10mg with the polyaniline foam of 1mol/l doped hydrochlorides and the Mg paper tinsels of 30mg under the pressure of 2MPa, be made diameter
=1cm, the disk of thickness=1mm, so as to obtain, without additional electrolytic cell, then battery being placed in the ring of 80% relative humidity
In border, electricity and Hydrogen collection are carried out in a closed container with the discharge rate of 0.05 mA, collect result and see Fig. 8, received
Acquisition means are shown in Fig. 9.
Embodiment 10
By 10mg with the polyaniline foam of 1mol/l doped hydrochlorides and the Mg paper tinsels of 30mg under the pressure of 2MPa, be made diameter
=1cm, the disk of thickness=1mm, so as to obtain, without additional electrolytic cell, battery then being placed in into different humidity environments
In, the relation of its open-circuit voltage and humidity is tested, its result is shown in Figure 10.
Embodiment 11
By 10mg with the polyaniline foam of 1mol/l doped hydrochlorides and the Mg paper tinsels of 30mg under the pressure of 2MPa, be made diameter
So as to obtain producing hydrogen battery without additional electrolyte, then be placed in battery in the aqueous solution by=1cm, the disk of thickness=1mm, surveys
The relation of its open-circuit voltage and oxygen content is tried, its result is shown in Figure 11.
Embodiment 12
By 10mg with the polythiophene foam of 1mol/l doped hydrochlorides and the Mg paper tinsels of 30mg under the pressure of 2MPa, be made diameter
=1cm, the disk of thickness=1mm, so as to obtain producing hydrogen battery without additional electrolyte, battery then is placed in into relative humidity is
In 80% environment, discharge test is carried out with the discharge rate of 0.1mA, its quality specific capacitance and specific energy are respectively 875.6
MAh/g, 160.5mWh/g.
Embodiment 13
By 10mg with the polypyrrole foam of 1mol/l doped hydrochlorides and the Mg paper tinsels of 30mg under the pressure of 2MPa, be made diameter
=1cm, the disk of thickness=1mm, so as to obtain producing hydrogen battery without additional electrolyte, battery then is placed in into relative humidity is
In 80% environment, discharge test is carried out with the discharge rate of 0.1mA, its quality specific capacitance and specific energy are respectively 565.6
MAh/g, 310.1mWh/g.
Embodiment 14
By 10mg with the polyaniline foam of 1mol/l doped hydrochlorides and the Zn paper tinsels of 30mg under the pressure of 2MPa, be made diameter
=1cm, the disk of thickness=1mm, so as to obtain producing hydrogen battery without additional electrolyte, battery then is placed in into relative humidity is
In 80% environment, discharge test is carried out with the discharge rate of 0.1mA, its quality specific capacitance and specific energy are respectively 910.6
MAh/g, 97.3mWh/g.
Comparative example 1
By 10mg with the polyaniline powder of 1mol/l doped hydrochlorides and the Mg paper tinsels of 30mg under the pressure of 2MPa, be made diameter
=1cm, the disk of thickness=1mm, so as to obtain without additional electrolytic cell, it is 80% that battery then is placed in into relative humidity
In environment, discharge test is carried out with the discharge rate of 0.1mA, its quality specific capacitance and specific energy are respectively 20.6 mAh/g,
20.5mWh/g。
Claims (3)
1. it is a kind of without additional electrolytic cell, it is characterised in that the battery is formed by positive pole and the compacting of negative pole directly contact：
Negative material is a kind of metal material with electro-chemical activity；The metal material is in magnesium, zinc, iron, aluminium, calcium or lithium
One or more；Positive electrode has electronic conductivity and ionic conductivity difference for a kind of, and has spongy electrification
Learn active polyaniline；
The preparation method without additional electrolytic cell positive pole is comprised the following steps：
S1. co-cable transmission blend is prepared：By polymethyl methacrylate, polystyrene, polyethylene, polypropylene, polybutene or
In makrolon at least two carry out melt blending；
S2. standard batten is prepared：The particle of the blend is carried out molded；
S3. co-cable transmission sample is prepared：The swelling foaming of standard batten is obtained；
S4. template is prepared：By the co-continuous single-phase extracting of sample, the mould of the polymer blend three-dimensional network with through-hole structure is obtained
Plate；
S5. the positive pole is obtained：Prepare two kinds of solution As, B, solution A：Ammonium persulfate is dissolved in ethanol water, solution B:Acid is molten
Liquid, aniline and deionized water mixture；Added after solution B is cooled to below 4 DEG C by the template of alkaline solution treatment, stirred
Mix, be slowly added to solution A, react 4~6h, oven drying 24h, remove the template, freeze-drying, obtain porosity 99% with
On co-cable transmission blend positive pole.
2. according to claim 1 without additional electrolytic cell, it is characterised in that the method for the preparation template includes adopting
Use supercritical CO2Foaming technique, addition are chemically or physically in foaming agent, phase separation, orientation freezing or solvent selectivity dissolving
One or more.
3. described in a kind of claim 1 without additional electrolytic cell application method, it is characterised in that the environmental wet for using
More than 40% or be placed directly in the battery in the aqueous solution by degree.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410462163.1A CN104377374B (en) | 2014-09-11 | 2014-09-11 | One kind is without additional electrolytic cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410462163.1A CN104377374B (en) | 2014-09-11 | 2014-09-11 | One kind is without additional electrolytic cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104377374A CN104377374A (en) | 2015-02-25 |
| CN104377374B true CN104377374B (en) | 2017-07-07 |
Family
ID=52556136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410462163.1A Active CN104377374B (en) | 2014-09-11 | 2014-09-11 | One kind is without additional electrolytic cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104377374B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105275A (en) * | 1985-07-05 | 1987-04-01 | 昭和电工株式会社 | Secondary cell |
| CN1037053A (en) * | 1988-04-13 | 1989-11-08 | 陆桂林 | Simple and easy manufacturing technology of high-energy conductive plactics storage battery |
| CN1037618A (en) * | 1988-05-06 | 1989-11-29 | 陆桂林 | Simple manufacturing technique of ordinary accumulator with conducting plastic anode |
| CN101752628A (en) * | 2010-01-21 | 2010-06-23 | 浙江大学 | Rechargeable metal hydride air cell |
| CN101794907A (en) * | 2009-11-20 | 2010-08-04 | 无锡欧力达新能源电力科技有限公司 | Aluminium polymer secondary battery and preparation method thereof |
| CN102088075A (en) * | 2009-12-07 | 2011-06-08 | 中国科学院化学研究所 | Electrode material of conductive polyaniline composite membrane and preparation method thereof |
| CN102544522A (en) * | 2012-01-11 | 2012-07-04 | 复旦大学 | Composite air electrode of lithium air cell and preparation method thereof |
| CN103545524A (en) * | 2013-09-23 | 2014-01-29 | 哈尔滨工业大学（威海） | Zinc-polyaniline cell and preparation method thereof |
| CN103928714A (en) * | 2014-04-30 | 2014-07-16 | 南京安普瑞斯有限公司 | Method for in-situ polymerization of conductive polyaniline in lithium ion battery pole group |
-
2014
- 2014-09-11 CN CN201410462163.1A patent/CN104377374B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105275A (en) * | 1985-07-05 | 1987-04-01 | 昭和电工株式会社 | Secondary cell |
| CN1037053A (en) * | 1988-04-13 | 1989-11-08 | 陆桂林 | Simple and easy manufacturing technology of high-energy conductive plactics storage battery |
| CN1037618A (en) * | 1988-05-06 | 1989-11-29 | 陆桂林 | Simple manufacturing technique of ordinary accumulator with conducting plastic anode |
| CN101794907A (en) * | 2009-11-20 | 2010-08-04 | 无锡欧力达新能源电力科技有限公司 | Aluminium polymer secondary battery and preparation method thereof |
| CN102088075A (en) * | 2009-12-07 | 2011-06-08 | 中国科学院化学研究所 | Electrode material of conductive polyaniline composite membrane and preparation method thereof |
| CN101752628A (en) * | 2010-01-21 | 2010-06-23 | 浙江大学 | Rechargeable metal hydride air cell |
| CN102544522A (en) * | 2012-01-11 | 2012-07-04 | 复旦大学 | Composite air electrode of lithium air cell and preparation method thereof |
| CN103545524A (en) * | 2013-09-23 | 2014-01-29 | 哈尔滨工业大学（威海） | Zinc-polyaniline cell and preparation method thereof |
| CN103928714A (en) * | 2014-04-30 | 2014-07-16 | 南京安普瑞斯有限公司 | Method for in-situ polymerization of conductive polyaniline in lithium ion battery pole group |
Non-Patent Citations (2)
| Title |
|---|
| 新型 Mg/导电 PANI 海水激活电池性能研究;邓姝皓等;《船电技术》;20071231;第27卷(第6期);第334-338页 * |
| 锂水电池技术研究进展;桑林等;《电源技术》;20140930;第38卷(第9期);第1753-1757页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104377374A (en) | 2015-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103236560B (en) | A kind of sulfur/carbon composite anode material of lithium-sulfur cell and its preparation method and application | |
| CN102142538B (en) | Lithium ion battery electrode made of graphene/ MoS2 and amorphous carbon and preparation method | |
| CN102280640B (en) | Novel anode material for lithium-ion secondary battery | |
| CN103500826B (en) | A kind of preparation method of positive composite material of graphene-lithium battery | |
| CN103337631B (en) | Improve lithium titanate high-rate discharge ability and suppress the carbon nitrogen of aerogenesis to be total to method for coating | |
| CN107154486A (en) | A kind of cupric multi-element metal sulfide is the sodium-ion battery of negative material | |
| CN106252663B (en) | Metal-organic framework materials CuBDC nanometer sheet and its preparation method and application | |
| CN106981371A (en) | A kind of water system electrolyte super capacitance cell | |
| CN104037440B (en) | In a kind of acid solution without direct alcohol fuel battery of film and preparation method thereof | |
| CN103427068B (en) | A kind of positive electrode and preparation method thereof for lithium-sulfur cell | |
| CN107887594A (en) | A kind of compound lithium-rich manganese-based anode material and preparation method for lithium ion battery | |
| CN105218992A (en) | Sulfonated graphene metal-salt solid polymer electrolyte and its preparation method and application | |
| CN102916195A (en) | Graphene-coated copper oxide composite cathode material and method for manufacturing same | |
| CN107069133B (en) | A kind of method of lithium in recycling lithium cell cathode material | |
| CN104466122B (en) | Method for preparing nickel positive electrode of nickel-metal hydride secondary battery by using cobalt-aluminum hydrotalcite and application thereof | |
| CN106853968A (en) | A kind of preparation method of multielement codope lead carbon battery activated carbon | |
| CN108365172A (en) | A kind of lithium an- ode material and its preparation method and application of natural polymers protection | |
| CN110943258A (en) | PVDF-HFP composite lignocellulose gel polymer electrolyte membrane and preparation method thereof | |
| CN109802131A (en) | Lithium ion battery and its negative electrode tab and negative electrode material and preparation process | |
| CN103606680A (en) | Preparation method of natural graphite composite N-doped carbon nanofibers webs cathode material | |
| CN103606646B (en) | Nickel sulphur positive pole of a kind of lithium-sulfur cell and preparation method thereof | |
| CN104124435A (en) | Multi-edge MoS2 nanosheet/graphene electrochemical sodium storage composite electrode and preparation method | |
| CN104091915A (en) | Electrochemical sodium storage composite electrode with high capacity and cycle stability and preparation method | |
| CN108923033B (en) | Preparation method of porous carbon cathode material of lithium-sulfur battery based on phase transfer method | |
| CN104377374B (en) | One kind is without additional electrolytic cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |