CN103299454A - Method for producing electrodes for lithium-sulphur batteries - Google Patents

Method for producing electrodes for lithium-sulphur batteries Download PDF

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CN103299454A
CN103299454A CN2012800052024A CN201280005202A CN103299454A CN 103299454 A CN103299454 A CN 103299454A CN 2012800052024 A CN2012800052024 A CN 2012800052024A CN 201280005202 A CN201280005202 A CN 201280005202A CN 103299454 A CN103299454 A CN 103299454A
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sugar
carbon
electrode
sulphur
weight
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A·加祖赫
K·莱特纳
T·J·科普林
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BASF SE
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • 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
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/621—Binders
    • 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
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a method for producing electrodes for lithium-sulphur batteries. The present invention relates to a method for producing a cathode, characterised in that the following are mixed: (A) sulphur, (B) carbon modified to be electrically conductive and (C) at least one saccharide that is selected from monosaccharides, disaccharides, oligosaccharides and polysaccharides, and that is soluble or swellable in an acidic aqueous medium, the resulting mixture being applied to a planar carrier (D) and then optionally dried.

Description

Produce the lithium-sulfur cell group method of electrode
The present invention relates to a kind of method of producing negative electrode, it comprises mixing:
(A) sulphur,
(B) be and conduct electricity the carbon of polymorph, and
(C) at least a sugar that is selected from monose, disaccharides, oligosaccharides and polysaccharide, it can dissolve or swelling in acidic aqueous media,
Reach the gained mixture is put on flat carrier (D) upward and randomly makes its drying subsequently.
The invention further relates to electrode, it comprises:
(D) at least one flat carrier,
And the mixture of following each material is thereon:
(A) sulphur,
(B) be and conduct electricity the carbon of polymorph, and
(C) at least a sugar that is selected from monose, disaccharides and polysaccharide, it can dissolve or swelling in acidic aqueous media.
Secondary battery, storage battery or " rechargeable battery " only are store electrical energy and use some embodiment of (consumption) electric energy when needed after producing electric energy.Because much better power density, R﹠D direction is transferred to the battery pack of being finished charge transport by lithium ion by water base secondary battery recently.
Yet, have carbon anode and limited based on the energy density of the conventional lithium-ions battery of the negative electrode of metal oxide.The opened new visual field of lithium-sulfur cell.In lithium-sulfur cell, the sulphur in the sulphur negative electrode is reduced to S via the polysulfide ion 2-Ion, it is reoxidized when battery charge.
Yet, often observe sulphur and be distributed on the electrode brokenly.It can cause unfavorable character, for example the loose contact of sulphur and therefore cause low electrode utilance.These defectives can cause electrode to have low electric capacity and/or capacitance loss.
Therefore, the object of the invention is for providing the lithium-sulfur cell of avoiding this problem.Another object of the present invention is provides a kind of production not have the method for the lithium-sulfur cell of above-mentioned defective.
Correspondingly, found to start the method for definition.
Sulphur (A) itself is known and also can abbreviate sulphur as in the context of the invention.
In the context of the invention, be and conduct electricity the carbon (B) of polymorph and also can be described as carbon (B).Carbon (B) can be selected from for example mixture of graphite, carbon black, carbon nano-tube, Graphene or at least two kinds of above-mentioned substances.
In one embodiment of the invention, carbon (B) is carbon black.That carbon black can for example be selected from is dim, furnace black, flame carbon black (flame black), thermal black, acetylene black and industrial carbon black (industrial black).Carbon black can comprise impurity, for example hydrocarbon (especially being aromatic hydrocarbon) or oxygenatedchemicals or oxy radical (for example OH group).In addition, may there be sulfur-bearing or ferrous contaminants in the carbon black.
In a modification, carbon (B) is the carbon black of partial oxidation.
In one embodiment of the invention, carbon (B) comprises carbon nano-tube.Carbon nano-tube (abbreviating CNT as), for example Single Walled Carbon Nanotube (SW CNT) and preferred multi-walled carbon nano-tubes (MW CNT) itself are known.Its preparation method and some characteristic for example are described in Chemie Ingenieur Technik 2006,78 by people such as A.Jess, among the 94-100.
In the context of the invention, should understand Graphene and almost mean the two-dimensional hexagonal carbon crystal that has with the similar structure of indivedual graphite linings ideally or ideally.
In a preferred embodiment of the invention, carbon (B) is selected from graphite, Graphene, activated carbon and carbon black especially.
Carbon (B) can for example exist with the particulate forms with the diameter in 0.1 μ m to 100 μ m, preferred 2 μ m to 20 mu m ranges.Should understand the average diameter that particle diameter means secondary, namely be decided to be the volume averaging value.
In one embodiment of the invention, measured according to ISO 9277, carbon (B) and especially carbon black have at 20m 2/ g to 1500m 2BET surface area in the/g scope.
In one embodiment of the invention, mix at least two kinds of (for example two or three) different types of carbon (B).Different types of carbon (B) is difference aspect particle diameter or BET surface area or dustiness for example.
In one embodiment of the invention, selected carbon (B) is the combination of carbon black and graphite.
Another initial substance of implementing the inventive method is at least a sugar (C) that is selected from monose, disaccharides, oligosaccharides and polysaccharide, and this sugar can dissolve or swelling in the aqueous acidic medium, also abbreviates sugar (C) as.The sugar that dissolves in the acidic aqueous media is preferred.
Should understand acidic aqueous media means and has the aqueous solution that is no more than 6.9 pH value (for example in 1 to 6.9 scope, preferably the pH value in 3 to 6.5 scopes).
Dissolve in the alkaline water-bearing media, but in acidic aqueous media neither swellable again insoluble acetylcellulose be not the example of sugar (C).Starch also in the aqueous acidic medium neither swellable can not dissolve and in the context of the invention, be not the sugar example of (C) again.
In the context of the invention, should understand " water-soluble " sugar compounds and mean the clearly visible sugar compounds that can in acidic aqueous media, form solution of naked eyes.In the context of the invention, should understand " water swellable " sugar compounds and mean under the temperature in 20 ℃ to 90 ℃ scopes the sugar compounds of the water of reversible absorption own wt at least 100%.
In one embodiment of the invention, sugar (C) is selected from glucose, fructose, sucrose, mannose and maltose.
In one embodiment of the invention, sugar (C) is selected from monose, especially glucose and fructose.
In one embodiment of the invention, sugar (C) is selected from disaccharides, especially sucrose.
In one embodiment of the invention, sugar (C) is selected from polysaccharide, especially amylopectin.
In one embodiment of the invention, sugar (C) is selected from the sugar of partial oxidation, the especially monose of partial oxidation or disaccharides, especially caramel, for example caramelization sucrose, caramelization glucose and caramelization fructose.
The program of implementing the inventive method is mixed with each other at first making sulphur (A), carbon (B) and at least a sugar (C), and can put on flat carrier (D) upward and make its drying subsequently by thus obtained mixture.
Mixing can be implemented by known method itself, for example by grinding sulphur (A), carbon (B) and at least a sugar (C) together, especially implement in grinding in ball grinder, or by in aqueous suspension, stirring sulphur (A), carbon (B) and at least a sugar (C) together.Also can under the situation of adding water, mediate sulphur (A), carbon (B) and at least a sugar (C), obtain aqueous paste.Preferably make at least two kinds of mixed method combinations with one another.Program is most preferably ground sulphur (A), carbon (B) and at least a sugar (C) together, for example in grinding in ball grinder, and it is suspended in water or the aqueous formulation.Of the present invention another extremely in the preferred embodiment, at first sulphur (A), carbon (B) and at least a sugar (C) one are arised from the liquid, for example in water or in water/alcohol mixture, stir, and grind subsequently, for example in grinding in ball grinder.
In a modification of the inventive method, selected mixed method is ultrasonication.
Mixing resultant is for obtaining the mixture of sulphur (A), carbon (B) and at least a sugar (C), and it can have one or more other components, for example water or at least a organic solvent.
Mixture at sulphur (A), carbon (B) and at least a sugar (C) further wraps in the aqueous embodiment, also should mention aqueous formulation in the context of the invention.Aqueous formulation can be configured to pastel or ink.
Aqueous formulation can comprise in water for example 0.1 volume % until 70 volume %, especially at least a organic solvent of 5 volume % in 60 volume % scopes.Suitable organic solvent is for example water-soluble alcohol, especially methyl alcohol, ethanol and isopropyl alcohol.
In another embodiment of the present invention, aqueous formulation does not comprise any organic solvent.
In another embodiment of the present invention, the mixture of sulphur (A), carbon (B) and at least a sugar (C) neither comprises water and does not comprise organic solvent again, and is pulverulent mixture.
In the context of the invention, those the preferred aqueous formulations with the solids content in 1.1 weight % to 20 weight % scopes are called ink.Have above 20 weight % and be called pastel until those preferred aqueous formulations of the solids content of 45 weight %, preferred at least 20.1 weight %.
In one embodiment of the invention, pastel comprises:
Sulphur (A) in 12 weight % to 20 weight %, preferred 13 weight % to 15 weight % scopes,
Carbon (B) in 8 weight % to 20 weight %, preferred 8 weight % to 12 weight % scopes,
Sugar (C) in 0.1 weight % to 5 weight %, preferred 0.5 weight % to 3.0 weight % scope altogether,
Wherein in the numeral of weight % separately in whole pastel,
And the summation of the percentage by weight of sulphur (A), carbon (B) and sugar (C) surpasses 20, is preferably at least 20.1.
In one embodiment of the invention, ink comprises:
Sulphur (A) in 0.5 weight % to 10 weight %, preferred 3.0 weight % to 3.5 weight % scopes,
Carbon (B) in 0.5 weight % to 9 weight %, preferred 2.5 weight % to 3 weight % scopes,
Sugar (C) in 0.1 weight % to 1.0 weight %, preferred 0.3 weight % to 0.5 weight % scope altogether,
Wherein in the numeral of weight % separately in whole inks,
And the summation of the percentage by weight of sulphur (A), carbon (B) and sugar (C) is in 1.1 to 20 scope.
The mixture of the sulphur (A), carbon (B) and at least a sugar (C) that prepare in the first step put on the flat carrier (D) can be for example be coated with method, printing (especially passing through screen painting) or realize by compressing by spraying (for example spraying or atomizing) and scraper.In the context of the invention, atomizing also comprises by means of spray gun and applying, a kind of method that often is also referred to as " air-brush method " or is called for short " air-brush ".
If wish to put on the flat carrier (D) by the mixture of spraying with sulphur prepared in the first step (A), carbon (B) and at least a sugar (C), then preferably with the ink form preparating mixture.
If wish to be coated with method or to put on the flat carrier (D) by the mixture of screen painting with sulphur (A), carbon (B) and at least a sugar (C) produced in the first step by scraper, then preferably with the paste form preparating mixture.
In one embodiment of the invention, flat carrier (D) is the media of conduction current, for example output conductor.
In a preferred embodiment of the invention, flat carrier (D) is chemical inertness with respect to the reaction of carrying out in (also namely in charging process and in discharge process) electrochemical cell in the standard operation.
In one embodiment of the invention, flat carrier (D) has at 20m 2/ g to 1500m 2BET internal surface area in the/g scope, it is preferably with apparent BET surface area test.
In one embodiment of the invention, flat carrier (D) is selected from wire netting, for example steel mesh (especially stainless (steel) wire) and nickel screen or tantalum net.Wire netting can have gross porosity or pore.
In another embodiment of the present invention, flat carrier (D) is selected from conductive fabric, for example comprises the carbon of wire (for example tantalum wire or nickel wire) or underbed, felt or the non-woven fabric of organic polymer.
Specially suitable flat carrier (D) is for example metal forming, especially aluminium foil.Metal forming for example can have at 4 μ m to 200 μ m, the thickness in 20 μ m to 50 mu m ranges especially.
The form of flat carrier (D) can be selected in relative broad range, and for example being can be by the continuous strip form of battery pack manufacturer processing.In other embodiments, flat carrier (D) can be constructed for example rounded, ellipse or square sheets form, or is a cube form, or is the plane electrode form.
In one embodiment of the invention, for example under the pressure in 0.1 bar to 300 bar scope and the temperature in 0 ℃ to 150 ℃ scope, (D) is compressed with flat carrier for the mixture of sulphur (A), carbon (B) and at least a sugar (C).For this reason, can be by pastel or preferably begun by pulverulent mixture, regulate its layer height by means of the pad on the flat carrier (D).
In one embodiment of the invention, the mixture of sulphur (A), carbon (B) and at least a sugar (C) can put on a side of flat carrier (D).
In one embodiment of the invention, the mixture that comprises sulphur (A), carbon (B) and at least a sugar (C) only puts on a side of flat carrier.
In one embodiment of the invention, the mixture of sulphur (A), carbon (B) and at least a sugar (C) is put on the flat carrier (D), make at every layer that measures after the drying layer thickness in the scope of 30 μ m to 200 μ m, preferred 60 μ m to 120 μ m.
Optionally drying can be for example implemented under the temperature in 30 ℃ to 100 ℃ scopes, in preferred 40 ℃ to the 50 ℃ scopes.
Optionally drying can be under normal pressure or preferably under reduced pressure, for example implements under 1 millibar to 500 millibars.
The suitable equipment that is used for drying steps comprises refrigerator and especially comprises Vacuum refrigerator.
In one embodiment of the invention, the aqueous formulation that will comprise following material puts on the metal film and subsequent drying:
(A) sulphur,
(B) be and conduct electricity the carbon of polymorph, and
(C) at least a sugar (C).
Flat carrier (D) through being coated with can be used as the electrode in the electrochemical cell thus.
Certainly, can implement other steps for this purpose, for example be connected in output conductor.
Flat carrier (D) by the inventive method coating represents many advantages as the electrode in the electrochemical cell.Example comprises homogeneous sulphur content cloth, with the good combination of flat carrier (D) and contact and high utilization efficiency.
The present invention further provides electrode, it comprises:
(D) at least one flat carrier,
And the mixture of following each material is thereon:
(A) sulphur,
(B) be and conduct electricity the carbon of polymorph, and
(C) at least a sugar that is selected from monose, disaccharides and polysaccharide, it can dissolve or swelling in acidic aqueous media.
Sulphur (A), carbon (B) and sugar (C) are as hereinbefore defined.
In one embodiment of the invention, carbon (B) is selected from graphite, Graphene, carbon black and activated carbon, is preferably selected from carbon black.
In one embodiment of the invention, electrode of the present invention comprises at least two kinds of (for example two or three) different types of carbon (B).Different types of carbon (B) is difference aspect particle diameter or BET surface area or dustiness for example.
In one embodiment of the invention, sugar (C) is selected from glucose, fructose, sucrose, mannose and maltose.
In one embodiment of the invention, sugar (C) is selected from monose, especially glucose and fructose.
In one embodiment of the invention, sugar (C) is selected from disaccharides, especially sucrose.
In one embodiment of the invention, sugar (C) is selected from polysaccharide, especially amylopectin.
In one embodiment of the invention, sugar (C) is selected from the sugar of partial oxidation, the especially monose of partial oxidation or disaccharides, especially caramel, for example caramelization sucrose, caramelization glucose and caramelization fructose.
In one embodiment of the invention, with the flat carrier (D) of sulphur (A), carbon (B) and sugar (C) coating in drying by measuring every layer of thickness that has in 30 μ m to 200 μ m, preferred 60 μ m to 120 mu m ranges, also namely putting under the situation of both sides, gross thickness is 60 μ m to 400 μ m, preferred 120 μ m to 240 μ m.
Electrode of the present invention especially is suitable for the member of making to contain the lithium battery group.The invention provides electrode of the present invention as the electrochemical cell member or for the production of the purposes of electrochemical cell.The present invention further provides the electrochemical cell that comprises at least one electrode of the present invention.
In one embodiment of the invention, electrode of the present invention is negative electrode, and it also can be described as sulphur negative electrode or S negative electrode.In the context of the invention, be called the electrode of negative electrode for the electrode of reduction reaction takes place in discharge process.
Electrode of the present invention can have the thickness in for example 60 μ m to 230 μ m, preferred 90 μ m to 150 mu m ranges.It can for example have club shaped structure, or constructs rounded, ellipse or square column form, or is a cube form, or is configured to plane electrode.
In one embodiment of the invention, electrochemical cell of the present invention also comprises the electrode that at least one comprises lithium metal or lithium alloy (for example alloy of lithium and tin, silicon and/or aluminium) except electrode of the present invention.
In one embodiment of the invention, except comprising electrode of the present invention and another electrode, electrochemical cell of the present invention also comprises at least a nonaqueous solvents that at room temperature can be liquid or solid, and it is preferably selected from polymer, cyclic ethers or acyclic ether, ring-type and non-annularity acetal, ring-type or non-annularity organic carbonate and ionic liquid.
The example of suitable polymer is PAG especially, is preferably poly-C 1-C 4Aklylene glycol and especially be polyethylene glycol.These polyethylene glycol can comprise 20mol% at the most one or more be the C of copolymerized form 1-C 4Aklylene glycol.PAG is preferably the PAG by methyl or the two end-blockings of ethyl.
The molecular weight M of suitable PAG and especially suitable polyethylene glycol wCan be 400g/mol at least.
The molecular weight M of suitable PAG and especially suitable polyethylene glycol wCan be 5 000 000g/mol at the most, preferably 2 000 000g/mol at the most.
The example of suitable acyclic ether for example is diisopropyl ether, di-n-butyl ether, 1,2-dimethoxy-ethane, 1, and the 2-diethoxyethane, preferred 1, the 2-dimethoxy-ethane.Other suitable acyclic ethers are diethylene glycol dimethyl ether, triglyme, tetraethylene glycol dimethyl ether, diethyl carbitol, triethylene glycol diethyl ether and tetraethylene glycol diethyl ether.
The example of suitable cyclic ethers is oxolane and 1,4-two
Figure BDA00003502107400082
Alkane.
The example of suitable non-annularity acetal is for example dimethoxymethane, diethoxymethane, 1,1-dimethoxy-ethane and 1,1-diethoxyethane.
The example of suitable cyclic acetal is 1,3-two
Figure BDA00003502107400083
Alkane and especially be 1,3-dioxolane.
The example of suitable non-annularity organic carbonate is dimethyl carbonate, ethyl carbonate methyl esters and diethyl carbonate.
The example of suitable cyclic organic carbonates is general formula (I) and compound (II):
Figure BDA00003502107400081
R wherein 1, R 2And R 3Can be identical or different, and be selected from hydrogen and C 1-C 4Alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl and the tert-butyl group, wherein preferred R 2And R 3Be not the tert-butyl group entirely.
In particularly preferred embodiments, R 1Be methyl and R 2And R 3Respectively be hydrogen, or R 1, R 2And R 3Respectively be hydrogen.
Solvent preferably uses under known anhydrous state, and namely water content is 1ppm to 0.1 weight %, and it can for example be determined by the Ka Er Karl Fischer titration.
In one embodiment of the invention, electrochemical cell of the present invention comprises one or more conducting salts, preferred lithium salts.The example of suitable lithium salts is LiPF 6, LiBF 4, LiClO 4, LiAsF 6, LiCF 3SO 3, LiC (C nF 2n+1SO 2) 3, imide li such as LiN (C nF 2n+1SO 2) 2(wherein n is the integer of 1-20), LiN (SO 2F) 2, Li 2SiF 6, LiSbF 6, LiAlCl 4And general formula (C nF 2n+1SO 2) mThe salt of XLi, wherein m is defined as follows:
M=1 when X is selected from oxygen and sulphur,
M=2 when X is selected from nitrogen and phosphorus, and
M=3 when X is selected from carbon and silicon.
Preferred conducting salt is selected from LiC (CF 3SO 2) 3And LiN (CF 3SO 2), preferred especially LiN (CF 3SO 2) 2
In one embodiment of the invention, the electrolyte of electrochemical cell of the present invention can comprise one or more additives, for example one or more ionic liquids.
In one embodiment of the invention, electrochemical cell of the present invention comprises the dividing plate of one or more mechanical separate mesh electrodes.Suitable dividing plate is thin polymer film, especially is porous polymer film, and it is to lithium metal and lithium sulfide and many lithium sulfides anergy.Especially the suitable material of dividing plate is polyolefin, especially is the porous polypropylene that is the porous polyethylene of form of film and is form of film.
The porosity of the dividing plate of being made, especially being made by polyethylene or polypropylene by polyolefin can be 35-45%.Suitable pore diameter for example is 30-500nm.
In another embodiment of the present invention, the dividing plate that selected dividing plate can be served as reasons and be made through inorganic particle filled PET non-woven fabric.The porosity of this dividing plate can be 40-55%.Suitable pore diameter is for example 80-750nm.
Even battery of the present invention still keeps high-effect behind recharge owing to electric capacity is especially high and battery failure significantly postpones to merit attention.Battery of the present invention is suitable in automobile, aircraft, boats and ships or the fixed energies storage very much.This purposes form theme of the present invention another part.
The present invention illustrates by work embodiment.
General preliminary note: in the context of the invention, unless clearly statement in addition, otherwise in the numeral of percentage based on percentage by weight.
Use following carbon black:
Carbon black (B.1), with
Figure BDA00003502107400101
Commercially available, BET surface area: 900m 2/ g (measuring according to ISO 9277), mean particle diameter: 10 μ m
Carbon black (B.2), with
Figure BDA00003502107400102
Commercially available, BET surface area: 100m 2/ g (measuring according to ISO 9277), mean particle diameter: 10 μ m
I. produce aqueous formulation
I.1 produce moisture ink WT1.1
In vial, stir 0.26g caramelization sucrose (C.1) in 73.5g water-isopropanol mixture (weight ratio: the solution 65:35).Subsequently, add 2.8g flowers of sulfur (A.1), 1g carbon black (B.1) and 1g carbon black (B.2), and continue to stir.In ball mill (from the Pulverisette6 of Fritsch), grind the period of going through under 300rpm 30 minutes can thus obtained suspension.After this, remove ball milling to obtain moisture ink, it is also referred to as WT1.1 hereinafter and has the creaminess denseness.
I.2 produce moisture ink WT1.2
In vial, stir the amylopectin aqueous solution (C.2) of 8.54g3 weight % in 77.5g water-isopropanol mixture (weight ratio: the solution 65:35).Subsequently, add 2.73g flowers of sulfur (A.1), 1g carbon black (B.1) and 1g carbon black (B.2), and continue to stir.In ball mill (from the Pulverisette6 of Fritsch), grind the period of going through under 300rpm 30 minutes can thus obtained suspension.After this, remove ball milling to obtain moisture ink, it is also referred to as WT1.2 hereinafter and has the creaminess denseness.
II. production electrode of the present invention
II.1 applies ink WT1.1 of the present invention and production electrode electr.1 of the present invention
Employed substrate is aluminium foil, and 30 μ m are thick.Subsequently, on vaccum bench, under 75 ℃ temperature, with spray gun ink WT1.1 of the present invention is sprayed on the aluminium foil, and uses nitrogen to spray.Summation based on (A.1), (B.1) and (C.1) is calculated, and obtains a side and is coated with 4mg/cm 2The aluminium foil of coating.
After this, between two rubber rollers modestly lamination one side through the coating aluminium foil.Select low contact pressure so that the coating retaining porosity.
After this heat treatment in drying box, temperature: 40 ℃.
Obtain electrode electr.1 of the present invention thus.
II.2 applies ink WT1.2 of the present invention and production electrode electr.2 of the present invention
Repeat example II.1 to obtain electrode electr.2 of the present invention, difference is to use ink WT1.2 of the present invention, rather than ink WT1.1 of the present invention.
III. production electrochemical cell of the present invention and test
Electrochemical Characterization about electrode electr.1 of the present invention and electr.2 makes up electrochemical cell according to Fig. 1.For this reason, except electrode of the present invention, also use with lower member:
Anode: the Li paper tinsel, thickness 50 μ m,
Dividing plate: polyethylene film, thickness 15 μ m, porous
According to the negative electrode of example II,
Electrolyte: the LiN (SO of 8 weight % 2CF 3) 2, 46 weight % 1,1 of 3-dioxolane and 46 weight %, 2-dimethoxy-ethane.
Fig. 1 is shown as the schematic construction of the electrochemical cell dismantled of test electrode of the present invention.
Note among Fig. 1 means:
1,1' mould
2,2' nut
3,3' sealing ring-all have two in each situation, second less in each situation sealing ring is not shown herein
4 helical springs
5 output conductors of being made by nickel
6 shells
Obtain electrochemical cell EZ.1 of the present invention (based on electrode electr.1 of the present invention) or electrochemical cell EZ.2 of the present invention (based on electrode electr.2 of the present invention).
Electrochemical cell of the present invention represents 2.6 volts to 2.9 volts Open Circuit Potential.During discharge (C/10), cell potential decays to 2.2 volts to 2.3 volts (first plateaus) and decays to 2.0 volts to 2.1 volts (second plateaus) subsequently.Battery discharge is down to 1.7V and charging subsequently.During charging operations, cell potential rises to 2.2 volts, and makes battery charge until reaching till 2.5 volts.Then begin discharge operation again.The electrochemical cell of producing of the present invention reaches and surpasses 30 circulations, only has minimum capacitance loss.

Claims (13)

1. method of producing negative electrode, it comprises mixing:
(A) sulphur,
(B) be and conduct electricity the carbon of polymorph, and
(C) at least a sugar that is selected from monose, disaccharides, oligosaccharides and polysaccharide, it can dissolve or swelling in acidic aqueous media,
Reach the gained mixture is put on flat carrier (D) upward and randomly makes its drying subsequently.
2. according to the process of claim 1 wherein that carbon (B) is selected from graphite, Graphene, carbon black and activated carbon.
3. according to the method for claim 1 or 2, wherein sugar is selected from amylopectin.
4. according to the method for claim 1 or 2, wherein sugar is selected from glucose, fructose, sucrose, mannose and maltose.
5. according to each method among the claim 1-4, wherein sugar is selected from the sugar of partial oxidation.
6. according to each method among the claim 1-5, the aqueous formulation that wherein will comprise following each material puts on the metal film and subsequent drying:
(A) sulphur,
(B) be and conduct electricity the carbon of polymorph, and
(C) at least a sugar that is selected from monose, disaccharides and polysaccharide, it can dissolve or swelling in acidic aqueous media.
7. electrode, it comprises:
(D) at least one flat carrier,
And the mixture of following each material is thereon:
(A) sulphur,
(B) be and conduct electricity the carbon of polymorph, and
(C) at least a sugar that is selected from monose, disaccharides and polysaccharide, it can dissolve or swelling in acidic aqueous media.
8. according to the electrode of claim 7, wherein carbon (B) is selected from graphite, Graphene, carbon black and activated carbon.
9. according to the electrode of claim 7 or 8, wherein sugar is selected from amylopectin.
10. according to the electrode of claim 7 or 8, wherein sugar is selected from glucose, fructose, sucrose, mannose and maltose.
11. according to each electrode among the claim 7-10, wherein sugar is selected from the sugar of partial oxidation.
12. according to the purposes of each electrode among the claim 7-11, it is used for electrochemical cell.
13. an electrochemical cell, it comprises at least one according to each electrode among the claim 7-11.
CN2012800052024A 2011-01-13 2012-01-11 Method for producing electrodes for lithium-sulphur batteries Pending CN103299454A (en)

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