CN105190959A - Battery and method for producing same - Google Patents
Battery and method for producing same Download PDFInfo
- Publication number
- CN105190959A CN105190959A CN201380071671.0A CN201380071671A CN105190959A CN 105190959 A CN105190959 A CN 105190959A CN 201380071671 A CN201380071671 A CN 201380071671A CN 105190959 A CN105190959 A CN 105190959A
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- CN
- China
- Prior art keywords
- storage battery
- carbon
- anode
- zinc
- battery according
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a battery (10, 30), especially a zinc-air battery, comprising an anode (12, 12a), which contains zinc, and a cathode (14) in the form of an oxygen electrode, the anode (12, 12a) additionally containing carbon.
Description
Technical field
The present invention relates to the application of a kind of storage battery and manufacture method and the upperseat concept according to independent claims.
Background technology
In future, not only in the Mobile solution of such as mobile phone, notebook computer and computer and so on, and also will use more and more in the vehicle of such as motor vehicle driven by mixed power (English HEV represents motor vehicle driven by mixed power) and motor vehicle (English EV represents motor vehicle) and so on there is high particular energy or the battery system of energy density.
Applying safety and the requirement in useful life accordingly to meet, developing these battery systems further at present.
The target especially zinc air battery of current development activities all over the world.Compared with lithium-ions battery, zinc air battery can reach higher energy density or particular energy.Use metallic zinc (Zn) as anode at this, use oxygen electrode as negative electrode.Rechargeable zinc air battery is also under development at present, therefore not yet business application.
US20060269811A1 describes a kind of method extending zinc air battery useful life.This zinc air battery is made up of multiple storage battery list pond, is exposed to successively in surrounding air in these storage battery list ponds, makes a certain moment only activate a storage battery.The anode of storage battery is implemented as zinc anode, and negative electrode is implemented as oxygen electrode.
CN-101055933A describes another kind of such zinc air battery.
TW385559A describes the manufacture of the lithium-ions battery of the negative electrode having and be made up of lithium and nickel and the anode be made up of carbon and zinc.
US20090023065A1 describes a kind of be made up of carbon, metal and polymer, anode be applied in lithium-ions battery.
KR2011078307A describes a kind of lithium-ions battery with zinc anode.Use the metallic zinc scribbling carbon as active material.
US20100159328A1 discloses a kind of manufacture of the zinc antimony carbon anode for lithium-ions battery.
DE102007034178A1 discloses a kind of rechargeable lithium-ions battery.Use nanotube and/or embed nanostructure and be combined to the graphite of lithium and/or natural lithium as electro-chemical activity anode material.
DE102004014629A1 describes a kind of lithium-ions battery, its negative electrode contain can embed lithium graphite-like carbon modified as active material.The material with carbon element of negative electrode has the degree of crystallinity being less than 80%.
The zinc anode of current known metal generally all has little charge and discharge cycles stability.Zinc is spongy precipitation in charging process, and such as may react with electrolyte.In addition metallic zinc is separated out and also may be caused anode forms zinc-Dendritic TiC (Zink-Dendriten).Zinc-Dendritic TiC can through separator growth, therefore, it is possible to cause the internal short-circuit of storage battery, single pond excessive heating, even on fire or blast and so on safety problem.
Summary of the invention
Therefore task of the present invention is the storage battery and the manufacture method thereof that provide a kind of improvement, can avoid the above-mentioned shortcoming about service lifetime of accumulator and fail safe.Storage battery of the present invention comprises and improves cyclical stability and the anode that improve fail safe.
Storage battery of the present invention and manufacture method of the present invention have the feature described in independent claims, can solve task of the present invention in a beneficial manner.
This especially has the anode not only containing zinc but also carbon containing based on, storage battery.Carbon anode is conducive to zinc and moves into reversible manner and move out.Carbon forms at this basal body structure making anodic stabilization.In addition, carbon base body also prevents from consuming zinc by the zinc-Dendritic TiC of dispersion and electrolytical reversible reaction in charge and discharge cycles process.Charge and discharge cycles stability can be significantly improved by this way, especially can significantly improve the security feature in single pond of chargeable storage.
Other favorable embodiment of the present invention is described in dependent claims.
According to the particularly advantageous execution mode of one of the present invention, anode has the carbon modified embedding zinc.
Preferably, anode comprise zinc ion embed wherein by reversible electrochemical reaction or deintercalation, the carbon base body that namely can move into or move out.Zinc ion embeds and the dynamics of deintercalation is preferably high, therefore can realize the sufficiently high current capability in storage battery list pond and high cyclical stability.Preferably, this is supported by the high conductivity of carbon itself.In addition, the conductivity of carbon also can improve the conductivity of anode, and anode advantageously becomes has load capacity more.In addition when storage battery list pond load height electric current, the final cut-ff voltage in storage battery list pond can also advantageously be realized a little later, therefore, it is possible to improve the discharge capacity in storage battery list pond.
Owing to embedding the carbon modified of zinc on anode, therefore, it is possible to realize high initial power and fault offset fast, namely high pulse load ability.
In charge and discharge cycles process, zinc ion is moved into and is moved out in carbon base body.This can cause anode volume to change.Because carbon base body is highly stable, be conducive to avoiding or obviously reducing change in volume.Because the carbon modified embedding zinc makes anode have high cyclical stability, therefore, it is possible to extend the useful life in storage battery list pond.Compared with lithium-ions battery, these storage battery list ponds can realize higher particular energy or energy density.In addition owing to avoiding the zinc-Dendritic TiC that may occur, the security feature in chargeable storage battery list pond can also obviously be improved.Especially the danger of internal short-circuit is reduced.
In addition be favourable, anode contains the carbon of graphite, hard carbon, soft carbon or carbon nano-tube (English " Carbo-Nanotubes ", is abbreviated as CNT) form.
Graphite is made up of the two-dimensional graphene layer be mutually arranged under the overlay.Graphite is conducive to zinc and moves between graphene layer and move out.Produce highly stable structure by this way, thus improve the cyclical stability in storage battery list pond.Also be applicable to selecting such as hard carbon, soft carbon or carbon nano-tube to carry out alternative graphite.
In addition advantageously, the ratio that in anode, zinc and the amount of carbonizable substance become to divide is 1: 16 to the maximum.
The carbon number of graphite is preferably 16: 0.9 to 16: 1 with the ratio of the zinc atom number on graphene layer, has confirmed that especially favourable ratio is 16: 1.
The about low 10-30% of zinc-iron alloy solution energy force rate carbon of hard carbon, soft carbon or carbon nano-tube.The ratio that zinc becomes to divide with the amount of hard carbon, soft carbon or carbon nanotube material is preferably 0.7-0.9: 16.Although the energy density in storage battery list pond can be reduced by this way, be conducive to the useful life and the high current loads ability that improve storage battery list pond.
According to the particularly advantageous execution mode of one of the present invention, it is C that anode comprises a kind of chemical formula
16the organo-metallic compound of Zn.
Based on this specific composition, the charge/discharge cycle characteristics in storage battery list pond can be stablized significantly and extend its useful life.
In addition be favourable, the negative electrode of storage battery or oxygen electrode are also containing carbon black, electrically conductive graphite or carbon nano-tube.The carbon black that such as person's character height is unordered can improve the conductivity of negative electrode.In addition, high electric current advantageously can be born in negative electrode and storage battery list pond.
Other theme of the present invention is a kind of method for the manufacture of corresponding storage battery, and this storage battery has negative electrode or the anode containing zinc and carbon, and has positive electrode or be configured to the negative electrode of oxygen electrode.In addition the carbon of anode is loaded with zinc.
According to the first favourable execution mode of the present invention, first the anode with carbon is provided, loads this anode with zinc subsequently, thus produce the anode of storage battery.
At this, can use conventionally manufacture and the anode that therefore can buy as carbon anode, subsequently preferably by zinc embed anode carbon base body in mode make it load zinc.
Application in principle for the zinc of electrode is favourable, because the rich reserves of zinc and can reclaiming.
According to the second Advantageous embodiments of the present invention, first carry out preparation example as C by Rui Fuer MAERSK (Reformatzky)-synthetic method
16the carbon zinc compound of Zn form, is then applied on the separator as anode.
When charging in storage battery list pond, zinc atom is migrated on graphene layer or between graphene layer, and again move out from graphene layer when discharging.These reactions have rapid kinetics characteristic.Very high affinity is also had between this external zinc atom and graphene layer.Based on the rapid kinetics characteristic of reaction of moving into or move out, storage battery list pond has high high current loads ability.
In the discharge process in storage battery list pond, carry out following reaction at anode:
Scheme 12C
16zn+8OH
--> 2Zn (OH
-)
4 2-+ 4e
-+ 2C
16
Electrolyte
Scheme 22Zn (OH
-)
4 2--> 2ZnO+2H
2o+4OH
-
During discharge process, carry out following reaction at negative electrode:
Scheme 3O
2+ 2H
2o+4e
--> 4OH
-
The overall reaction of discharge process:
Scheme 42C
16zn+O
2+ 2H
2o-> 2ZnO+2H
2o+2C
16
During the charging process in storage battery list pond, carry out following reaction at anode:
Scheme 52C
16+ 2ZnO is (by 2Zn (OH
-)
4 2-)+2H
2o+4e
--> 2C
16zn+4OH
-
During charging process, carry out following reaction at negative electrode:
Scheme 64OH
--> O
2+ 2H
2o+4e
-
Global schema
Scheme 72C
16+ 2ZnO-> 2C
16zn+O
2
Battery-driven Mobile solution, such as vehicle or notebook computer can be advantageously used according to storage battery of the present invention, and/or at energy technology field, preferably use in static application.
Accompanying drawing explanation
Below will with reference to the accompanying drawings with following associated description, the present invention is explained in detail.Wherein:
Fig. 1 shows the schematic diagram of storage battery according to first embodiment of the invention, and
Fig. 2 shows the schematic diagram of the storage battery according to the second execution mode of the present invention.
Embodiment
Figure 1 shows that according to the first execution mode storage battery 10 of the present invention, the electrolyte 16 that this storage battery comprises anode 12, negative electrode 14 and is arranged between anode 12 and negative electrode 14.Such as by separator 18a, anode 12 and electrolyte 16 are separated.Such as by separator 18b, negative electrode 14 and electrolyte 16 are separated.
First anode 12 has the carbon of such as graphite, hard carbon, soft carbon or carbon nano-tube form under unshaped state.When then charging in storage battery list pond, zinc ion enters among carbon base body.Therefore anode has the carbon modified that can embed zinc.
The potassium hydroxide (KOH) of electrolyte 16 preferably containing 15-30% proportion.
Be with the difference of Fig. 1, the mode producing the anode 12a of storage battery 30 first prepares C
16zn compound, is then applied on the separator 18a as anode 12a.
First be C by Rui Fuer MAERSK-synthetic method preparative chemistry formula
16the zinc organic compound of Zn.The people such as such as Savoia just described this preparation method in 1985 in Pur & Appl.Chem. magazine the 57th volume the 12nd phase 1887-1896 page.
In order to prepare C
16the zinc organic compound of Zn form, first synthesizes potassium graphite C 8K, directly can synthesize from these elements according to scheme 8 at about 200 DEG C of temperature in the atmosphere of inert gases of argon gas formation.
Scheme 88C+K-> C8K.
C
16zn synthetic method is based on anhydrous zinc chloride (ZnCl
2) and potassium graphite (C
8k), synthesize in the organic solvent of the not hydrogeneous and oxygen of such as oxolane (Tetrahydrofuran) THF or 1,2-dimethoxy-ethane DME and so under argon atmosphere according to scheme 9.
Scheme 92C8K+ZnCl2-> ZnC16+2KCl
Then be C by chemical formula
16the zinc organic compound of Zn is applied on the separator 18a as anode 12a.
Storage battery according to the present invention can be used in the Mobile solution of such as mobile phone, notebook computer and computer and so on, also can be used for the vehicle of such as motor vehicle driven by mixed power and motor vehicle and so on.
Also can using the intermediate energy storage device of above-described storage battery 10,30 as regenerated energy.
Claims (13)
1. storage battery, it has the negative electrode (14) of anode (12,12a) containing zinc and oxygen electrode form, it is characterized in that, described anode (12,12a) is also containing carbon.
2. the storage battery according to any one of the claims, is characterized in that, described anode (12,12a) is containing the carbon modified embedding zinc.
3. storage battery according to claim 1, is characterized in that, containing graphite, hard carbon, soft carbon or carbon nano-tube in the anode (12,12a) of carbon containing.
4. the storage battery according to any one of the claims, is characterized in that, the ratio of zinc and carbon is 1: 16 to the maximum.
5. storage battery according to claim 1, is characterized in that, described anode (12,12a) is the organo-metallic compound of C16Zn containing chemical formula.
6. the storage battery according to any one of the claims, is characterized in that, described anode (12,12a) is made up of carbon and zinc.
7. the storage battery according to any one of the claims, is in its feature, and described negative electrode (14) is also containing carbon black, electrically conductive graphite or carbon nano-tube.
8. the storage battery according to any one of the claims, is characterized in that, described storage battery (10,30) is rechargeable.
9. for the manufacture of the method for storage battery, wherein, described storage battery has anode containing zinc and carbon (12,12a), and wherein, described storage battery has the negative electrode being constructed to oxygen electrode, it is characterized in that, is added to by zinc in the described carbon of described anode (12,12a).
10. the method for the manufacture of storage battery according to claim 9, is characterized in that, first provides the anode (12) of carbon containing, and then zinc is added to described anode.
11. methods for the manufacture of storage battery according to claim 10, is characterized in that, added in graphite anode by zinc.
12. methods for the manufacture of storage battery according to claim 9, it is characterized in that, first prepared the carbon zinc compound of C16Zn form by Rui Fuer MAERSK-synthetic method, and then described carbon zinc compound is applied to as on the separator (18a) of anode (12a).
13. application of storage battery according to any one of claim 1 to 8 in battery-driven vehicle and/or in energy technology.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102013201254.3 | 2013-01-28 | ||
| DE102013201254.3A DE102013201254A1 (en) | 2013-01-28 | 2013-01-28 | Battery and method of making the same |
| PCT/EP2013/074562 WO2014114385A1 (en) | 2013-01-28 | 2013-11-25 | Battery and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105190959A true CN105190959A (en) | 2015-12-23 |
| CN105190959B CN105190959B (en) | 2018-05-04 |
Family
ID=49639884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380071671.0A Expired - Fee Related CN105190959B (en) | 2013-01-28 | 2013-11-25 | Storage battery and its manufacture method |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN105190959B (en) |
| DE (1) | DE102013201254A1 (en) |
| FR (1) | FR3001583B1 (en) |
| WO (1) | WO2014114385A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4842963A (en) * | 1988-06-21 | 1989-06-27 | The United States Of America As Represented By The United States Department Of Energy | Zinc electrode and rechargeable zinc-air battery |
| CN101036251A (en) * | 2004-09-28 | 2007-09-12 | 塔迪兰电池有限公司 | Improved lithium cell and method of forming same |
| CN101978550A (en) * | 2008-03-19 | 2011-02-16 | 住友化学株式会社 | Electrode and battery having the same |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617242A (en) * | 1983-10-19 | 1986-10-14 | Rayovac Corporation | Organic siliconate additive for alkaline zinc electrochemical cells |
| IL100625A (en) * | 1992-01-10 | 1995-03-30 | Electric Fuel Ltd | Electrically and mechanically rechargeable zinc/air battery |
| JP3717085B2 (en) * | 1994-10-21 | 2005-11-16 | キヤノン株式会社 | Negative electrode for secondary battery, secondary battery having the negative electrode, and method for producing electrode |
| TW385559B (en) | 1998-04-03 | 2000-03-21 | Enegy Consortium Holdings Llc | Lithium battery and a method for manufacturing the lithium battery |
| DE102004014629A1 (en) | 2004-03-19 | 2005-10-06 | Varta Microbattery Gmbh | Galvanic element |
| US7611790B2 (en) | 2005-05-24 | 2009-11-03 | Robert Bosch Gmbh | Zinc/air battery with improved lifetime |
| CN101055933A (en) | 2006-04-11 | 2007-10-17 | 中国科学技术大学 | A Zn air battery device convenient for Zn pole replacement |
| KR101386163B1 (en) | 2007-07-19 | 2014-04-17 | 삼성에스디아이 주식회사 | Composite anode material, and anode and lithium battery using the same |
| DE102007034178A1 (en) | 2007-07-23 | 2009-01-29 | Dilo Trading Ag | Rechargeable lithium-ion cell for lithium battery, comprises electrochemically active mass of anode and cathode consisting of non-polymer, binder and nanostructured particles |
| KR101103104B1 (en) | 2008-12-23 | 2012-01-04 | 서울대학교산학협력단 | Preparation Method of ZnSb-C Composite and Anode Materials for Secondary Batteries Containing the Same Composite |
| KR101142533B1 (en) | 2009-12-31 | 2012-05-07 | 한국전기연구원 | Metal based Zn Negative Active Material and Lithium Secondary Battery Comprising thereof |
-
2013
- 2013-01-28 DE DE102013201254.3A patent/DE102013201254A1/en not_active Withdrawn
- 2013-11-25 CN CN201380071671.0A patent/CN105190959B/en not_active Expired - Fee Related
- 2013-11-25 WO PCT/EP2013/074562 patent/WO2014114385A1/en active Application Filing
-
2014
- 2014-01-23 FR FR1450554A patent/FR3001583B1/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4842963A (en) * | 1988-06-21 | 1989-06-27 | The United States Of America As Represented By The United States Department Of Energy | Zinc electrode and rechargeable zinc-air battery |
| CN101036251A (en) * | 2004-09-28 | 2007-09-12 | 塔迪兰电池有限公司 | Improved lithium cell and method of forming same |
| CN101978550A (en) * | 2008-03-19 | 2011-02-16 | 住友化学株式会社 | Electrode and battery having the same |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102013201254A1 (en) | 2014-07-31 |
| FR3001583A1 (en) | 2014-08-01 |
| CN105190959B (en) | 2018-05-04 |
| FR3001583B1 (en) | 2017-06-30 |
| WO2014114385A1 (en) | 2014-07-31 |
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