CN104300115A - Cathode of battery for lithium manganese oxide ion battery pack - Google Patents
Cathode of battery for lithium manganese oxide ion battery pack Download PDFInfo
- Publication number
- CN104300115A CN104300115A CN201410479023.5A CN201410479023A CN104300115A CN 104300115 A CN104300115 A CN 104300115A CN 201410479023 A CN201410479023 A CN 201410479023A CN 104300115 A CN104300115 A CN 104300115A
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- China
- Prior art keywords
- negative electrode
- active material
- cathode
- composition
- battery
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
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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
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- 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 cathode of a battery for a lithium manganese oxide ion battery pack, relates to a method for producing the cathode and a lithium manganese oxide ion battery pack comprising one or more batteries with the cathodes. The cathode comprises an electrolyte based on lithium manganese oxide salt and a non-aqueous electrolyte solvent, the cathode is based on a polymer composition, the polymer composition is obtained by a melting method without evaporation of the solvent and is a product obtained by thermal combination reaction of an active material and additives, the additives comprise a polymer binder and a conductive filler, and the cathode is characterized in that the binder is based on at least one crosslinked elastomer, the additives further comprise at least one non-volatile organic compound used in the electrolyte solvent and the weight percentage of the active material in the composition is greater than or equal to 90%.
Description
Technical field
The present invention relates to a kind of negative electrode that can be used for the battery of mangaic acid Li-ion batteries piles, relate to a kind of method of producing described negative electrode, and relate to a kind of mangaic acid Li-ion batteries piles, it contains one or more battery comprising described negative electrode.
Background technology
Have the lithium storage battery that two kinds main: lithium metal battery group, wherein, negative pole is by lithium preparation of metals (deposit in case at liquid electrolyte, its material causes safety issue); And Li-ion batteries piles, wherein lithium exists with ionic condition.
Li-ion batteries piles is made up of the coulomb electrode (Coulombic electrode) of the conduction of at least two opposed polarities, wherein, negative pole or anode (being generally made up of graphite), and positive pole or negative electrode (are generally made up of transition metal oxide, as the oxide of vanadium or cobalt, or be made up of lithiumation iron phosphate, described in US B1 6514640 or WO A1 2011/092283), between said electrodes, be placed with isolated part, described isolated part is made up of electrical insulator, electrical insulator is adsorbed with based on the cationic non-proton electrolyte of Li+, to guarantee the conductibility of ion.The electrode being used in these Li-ion batteries piles is made up of lithium salts usually, and the example of described lithium salts is as molecular formula LiPF
6, LiAsF
6, LiCF
3sO
3or LiClO
4, it is dissolved in a kind of mixture of nonaqueous solvents, as acetonitrile, oxolane or more conventional a kind of carbonic ester, and such as vinyl acetate or propylene.
The active material of the negative electrode of Li-ion batteries piles allows lithium reversibly enter into negative electrode or reversibly shift out from negative electrode, and the mass fraction of active material described in negative electrode is higher, and capacity is higher.Negative electrode also must contain a kind of conductive compound, such as carbon black, and, in order to provide enough mechanical cohesions, also containing a kind of polymeric binder.Therefore, Li-ion batteries piles is based in batteries charging and discharge process, and lithium ion reversibly exchanges between the anode and cathode, and for low-down weight, due to the advantage in the physical property of lithium, this battery pack has high energy density.
The production method that the negative electrode of Li-ion batteries piles is the most frequently used, comprise in order: dissolve and spread various cathode components to the step in solvent, obtained solution is coated with the step spread or be dispersed in metal collector, and the step of the described solvent of last evaporation.Multiple polymers binding agent can be used, in mentioned binding agent, PVDF (Kynoar) is preferably used to prepare, due to the existence of fluorine, it is easily compatible that itself and negative electrode (are greater than 4V) under high operating voltage, can also be, such as the polyacrylonitrile (PAN) of butyl polyacrylate dipping.
The method of with an organic solvent producing Li-ion batteries piles negative electrode has some shortcomings about environment and fail safe.Especially, in the case, need to evaporate a large amount of poisonous or inflammable organic solvents.
For the method using aqueous solvent to produce described negative electrode, its disadvantage is that negative electrode must be fully dry before use, and the water of known trace can affect the useful life of lithium storage battery.
Therefore, for Li-ion batteries piles, a kind of negative electrode is prepared in high expectations, and it does not use solvent to produce, and in this context, uses smelting process technology (such as extruding) to produce the negative electrode being used for Li-ion batteries piles and describes in the literature.
Unfortunately, with regard to lithium ion battery, these melting methods bring extreme difficulties, as is known, in the polymer composition of negative electrode, need the parts by weight of active material to be at least 80%, to have enough capacity in Li-ion batteries piles.But in this active material weight number situation, the viscosity of cathode polymer mixture becomes very high, the risk causing mixture overheated or once use reduce its mechanical cohesion.
Document USB26939383 describes extruding of a kind of polymer composition, polymer composition comprises poly-(glycidol ether) copolymer of poly-(ethylene oxide) poly-(propylene oxide), for Ionic conductivity polymer, described Ionic conductivity polymer is used for the solvent-free preparation of lithium polymer battery group negative electrode.But in the single cathode polymer component prepared in the document, active material weight number is only 64.5%.
Document USA5749927 discloses a kind of method by extruding continuous production lithium polymer battery group, described method comprises and electric conducting material and solid electrolyte composition being mixed with active material, described solid electrolyte composition comprises a kind of polymer, exceedes a kind of lithium salts of described polymer and ethylene carbonate/propylene carbonate mixture, in the publication, the parts by weight of active material in cathode polymer composition are also lower than 70%.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of a kind of method for the production of negative electrode, which overcome above mentioned all defect, and, the object of the invention can be realized, because the beat all discovery of inventor: if active material and comprise crosslinked elastomer substrates, the additive of conductive filler and non-VOC (boiling point namely under 1.013 × 105 Pa atmospheric pressure environment is more than 150 DEG C), heating chemical combination, without the need to evaporating solvent, the cathode polymer composition obtained can be used in Li-ion batteries piles, described Li-ion batteries piles contains an electrode based on lithium salts and nonaqueous solvents, the product that active material parts by weight in the composition obtain apparently higher than above-mentioned melting method, be highly profitable greater than or equal to 90%, one or more organic compounds are used as the solvent of described electrode valuably.
According to a kind of negative electrode of the present invention, comprise a kind of electrolyte based on mangaic acid lithium salts and nonaqueous electrolyte solvent, described negative electrode is based on a kind of polymer composition, described polymer composition passes through melting method, and do not need evaporating solvent and obtain, it is the product of hot combination reaction between a kind of active material and additive, described additive comprises a kind of polymeric binder and conductive filler, it is characterized in that, described binding agent is based at least one cross-linked elastomer, and described additive also comprises at least one for the non-VOC in described electrolyte solvent, the parts by weight of the described active material that described composition contains are more than or equal to 90%.
It should be noted that according in negative electrode of the present invention, the parts by weight that active material is very high ensure that gained battery or each battery of gained are heavy-duty battery, and the Li-ion batteries piles being therefore provided with these batteries is a kind of high performance battery.Should also be noted that described at least one cross-linked elastomer is in the composition dispersed, ensure that the mechanical performance of negative electrode.
It is beneficial that, described active material can comprise polyanion compound or the complex compound of at least one lithiumation, its operating voltage is lower than 4V, preferably covered by carbon, such as, the lithiated metal M phosphate (also referred to as phosphorylation olivine, phospholivine) that molecular formula LiMPO 4 represents, such as has the carbon coated lithiated metal M phosphate of molecular formula CLiMPO 4.
Especially, it should be noted that the active material being applied to the present composition can be made up of the granule of elementary carbon coated particle (elementary carbon coated particle) or the elementary carbon coated particle containing carbon covering or precipitation.
Preferably, described at least one elastomer is peroxyde crosslinked diene elastomer, is even more preferably the acrylonitrile-butadiene rubber (HNBR) of hydrogenation.Also preferably, described at least one elastomer parts by weight are in the composition between 1% to 5%.
Valuably, described at least one non-VOC can contain a kind of carbonic ester, and be preferably at least one carbonic acid alkene ester, as ethylene carbonate, it is preferably used in described electrolyte composition.
It should be noted that described carbonic ester, use as ethylene carbonate, be conducive to as follows: the filer content in (1) composition increases; (2) inherent risk about the toxicity of the VOC (VOC) prepared for tradition in the method for negative electrode is avoided, because carbonic ester is solid at room temperature product, has lower danger during use; And it is advantageous that the described at least one organic compound parts by weight be present in described composition can be between 0.1% to 5%.
It should be noted that the present invention allows required salt, with in negative electrode production process, operate described negative electrode by compound.
According to another characteristic of the invention, described additive can also comprise cross-linking system, cross-linking system in the composition parts by weight between 0.05% to 0.20%, and preferably include a kind of organic peroxide and a kind of crosslinking coagent (crosslinking co agent), in case described at least one elastomer is diene elastomer, as hydrogenated nitrile-butadiene rubber (HNBR).According to another characteristic of the invention, described conductive filler can be selected from the group be made up of carbon black, graphite, expanded graphite, carbon fiber, carbon nano-tube, Graphene and their mixture, and parts by weight are in the composition between 1% to 5%.According to a kind of method of producing negative electrode as defined above of the present invention, it is characterized in that, it comprises:
A) in banbury or extruder, without the need to evaporating solvent, active material described in melt compounded and described additive, described additive comprises described adhesive and solid-state described organic compound, to obtain the composition of described crosslinkable state, described active material preferably comprises at least one carbon and covers lithiated iron phosphates, and molecular formula is C LiFePO 4; And
B) described composition is cross-linked, and carries out thermoforming alternatively, to obtain described crosslinked composition.
According to another characteristic of the invention, step a) is implemented in the Powdered pre-composition of other component of described composition by adhesive described in chemical combination, such as, implements at banbury, 60 DEG C to 80 DEG C temperature.
According to another characteristic of the invention, step b) can be implemented by cross-linkable composition described in hot pressing.
It is advantageous that the method for the invention can also comprise step c): cross-linked composition described in rolling is to be deposited in metal collector, and use described metal collector, negative electrode is assembled.
According to Li-ion batteries piles of the present invention, comprise at least one battery, the anode of a described battery such as Graphite-based anodes, such as above-mentioned a defined negative electrode and based on lithium salts and the electrolyte based on nonaqueous solvents.
According to a further aspect in the invention, described negative electrode comprises metal collector, and the film prepared by described polymer composition with at least one contacts.
Embodiment
Further feature of the present invention, advantage and describe in detail by by read following unrestricted, consumption illustrational of the present invention exemplify embodiment explanation and clearly.
Embodiment 1
In Haacke banbury, under 70 DEG C of conditions, prepare a kind of cathode polymer composition, described composition comprises in the following component of parts by weight (%):
Various mixture is introduced in described banbury successively, and being the hydrogenated nitrile-butadiene rubber (HNBR adhesive) of crosslinkable diene elastomer form at the beginning, is then the pre-composition of the powder type of other said components.After chemical combination, hot pressing 10 minutes at 170 DEG C, meanwhile, makes binding agent be cross-linked, directly obtain the electrode that a kind of 1mm is thick, described electrode, on described current-collector after deposition, can be formed in the negative electrode in the battery of Li-ion batteries piles, use described current-collector, described negative electrode is assembled.Should be understood that, the parts by weight (higher than 93%) that in described negative electrode, active material is very high guarantee that gained battery or each battery are heavy-duty battery, and the Li-ion batteries piles therefore containing these batteries is high performance battery.
Claims (5)
1. the negative electrode for the battery of mangaic acid Li-ion batteries piles, comprise a kind of electrolyte based on mangaic acid lithium salts and nonaqueous electrolyte solvent, described negative electrode is based on a kind of polymer composition, described polymer composition passes through melting method, and do not need evaporating solvent and obtain, it is the product of hot combination reaction between a kind of active material and additive, described additive comprises a kind of polymeric binder and conductive filler, it is characterized in that, described binding agent is based at least one cross-linked elastomer, and described additive also comprises at least one for the non-VOC in described electrolyte solvent, the parts by weight of the described active material that described composition contains are more than or equal to 90%.
2. negative electrode according to claim 1, is characterized in that, described active material comprises polyanion compound or the complex compound of at least one lithiumation, and it has the operating voltage lower than 4V, and is preferably covered by carbon; Such as lithiated metal M phosphate, molecular formula is LiMPO4, and wherein, M is iron ion such as.
3. negative electrode according to claim 1 and 2, is characterized in that, described at least one elastomer is peroxyde crosslinked diene elastomer, is preferably hydrogenated nitrile-butadiene rubber (HNBR).
4. the negative electrode according to above-mentioned any one claim, is characterized in that, described at least one elastomer parts by weight are in the composition between 1% to 5%.
5. the negative electrode according to above-mentioned any one claim, is characterized in that, described at least one organic compound comprises carbonic ester, is preferably at least one carbonic acid alkene ester, as ethylene carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410479023.5A CN104300115A (en) | 2014-09-18 | 2014-09-18 | Cathode of battery for lithium manganese oxide ion battery pack |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410479023.5A CN104300115A (en) | 2014-09-18 | 2014-09-18 | Cathode of battery for lithium manganese oxide ion battery pack |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104300115A true CN104300115A (en) | 2015-01-21 |
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ID=52319762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410479023.5A Pending CN104300115A (en) | 2014-09-18 | 2014-09-18 | Cathode of battery for lithium manganese oxide ion battery pack |
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|---|---|
| CN (1) | CN104300115A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534800A (en) * | 2019-09-17 | 2019-12-03 | 清华大学 | A kind of method that low cost mass prepares Organic-inorganic composite solid electrolyte |
-
2014
- 2014-09-18 CN CN201410479023.5A patent/CN104300115A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534800A (en) * | 2019-09-17 | 2019-12-03 | 清华大学 | A kind of method that low cost mass prepares Organic-inorganic composite solid electrolyte |
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| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150121 |
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| WD01 | Invention patent application deemed withdrawn after publication |