CN107768654A - The preparation method of electrode composite material, positive pole, the battery with the positive pole - Google Patents

The preparation method of electrode composite material, positive pole, the battery with the positive pole Download PDF

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Publication number
CN107768654A
CN107768654A CN201711020262.4A CN201711020262A CN107768654A CN 107768654 A CN107768654 A CN 107768654A CN 201711020262 A CN201711020262 A CN 201711020262A CN 107768654 A CN107768654 A CN 107768654A
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China
Prior art keywords
composite material
electrode composite
preparation method
elemental sulfur
positive pole
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CN201711020262.4A
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Chinese (zh)
Inventor
陈璞
李晶
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苏州宝时得电动工具有限公司
陈璞
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Application filed by 苏州宝时得电动工具有限公司, 陈璞 filed Critical 苏州宝时得电动工具有限公司
Priority to CN201210418616.1A priority Critical patent/CN103794764A/en
Priority to CN201711020262.4A priority patent/CN107768654A/en
Publication of CN107768654A publication Critical patent/CN107768654A/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors

Abstract

The present invention relates to a kind of preparation method of electrode composite material, comprise the following steps:Raw material mixes, and dries, and obtains mixture, and raw material comprises at least elemental sulfur and polyacrylonitrile, and the percentage by weight of elemental sulfur is not less than 50%;Mixture carries out first time heating under the first protective atmosphere, obtains compound, heats elemental sulfur in atmosphere for the first time and is in saturation state;Compound carries out second under the second protective atmosphere and heated, and cooling, that is, obtains electrode composite material, and elemental sulfur is in undersaturated condition in second of heating atmosphere.The content of sulphur in material can preferably be controlled by preparing electrode composite material by this method, and so as to improve the chemical property of electrode composite material, obtained electrode composite material has good cycle life and high discharge capacity efficiency.The invention also discloses apply the positive pole of the electrode composite material and possess the battery of the positive pole.

Description

The preparation method of electrode composite material, positive pole, the battery with the positive pole

The application be the entitled electrode composite material that applicant proposed on October 26th, 2012 preparation method, Positive pole, the battery with the positive pole, the divisional application of the Chinese invention patent application of Application No. 2012101418616.1.

Technical field

The present invention relates to a kind of preparation method of electrode composite material.

The invention further relates to a kind of positive pole with electrode composite material made from the preparation method.

The invention further relates to a kind of battery with the positive pole.

Background technology

In recent years, it is with the development of science and technology, more and more prominent to the demand of the especially renewable green energy resource of the energy, battery Storage and conversion equipment as energy are just playing irreplaceable effect.Lithium ion battery has very high mass ratio because of it Energy and energy density per unit volume, extensive concern is attracted.Low cost, high-energy-density, long circulation life, green is secondary Battery is the emphasis of current lithium ion battery exploitation.

The positive electrode of commercialization at present is mainly lithium transition-metal oxide (such as cobalt acid of stratiform or spinel structure Lithium, LiMn2O4) and olivine structural LiFePO4 etc..Cobalt acid lithium (LiCoO2) theoretical capacity it is relatively large, 275mAh/g, But its price is high, has certain toxicity, and exothermal decomposition reactions easily occur when overcharging for the positive electrode, not only make battery capacity It is decreased obviously, while threat is also resulted in cell safety;LiMn2O4 (LiMn2O4) theoretical capacity be 148mAh/g, actual capacity Less than 130mAh/g, the stability of the positive electrode is bad, and lattice deformability is easily caused in charge and discharge process, causes circulation to be imitated Rate is relatively low;LiFePO4 (LiFePO4) theoretical capacity be 172mAh/g, the poorly conductive of the positive electrode so that battery Reversible capacity reduces.Above-mentioned conventional anode material for lithium-ion batteries capacity is not universal high, while also there are problems that, it is impossible to Meet that battery develops demand.

The theoretical specific capacity of elemental sulfur is 1675mAh/g, and the theory that battery is assembled into lithium metal can reach than energy 2600mAh/g, far above the positive electrode of commercialization at present, turn into the main trend that present battery develops.Elemental sulfur and contain The inorganic sulphide of sulphur, organic sulfur compound, polymeric organodisulfide, organic polysulfide, polysulfide polymerize for compound and carbon-sulphur Thing etc. is extensively concerned as the positive electrode of high power capacity, but these materials still be present.

First, the electric conductivity of elemental sulfur and sulfide in itself is very poor, need to add substantial amounts of conductive agent to increase its electric conductivity; Secondly, when elemental sulfur is as positive electrode active materials, although being deposited when fully charged when elementary sulfur present on positive pole and electric discharge completely Li2S is insoluble in polarity organic bath, but more lithium sulfides existing for part discharge and recharge positive pole are soluble in polarity Organic Electricity Xie Zhi, in addition, small molecule sulfide caused by polymeric organosulfides electric discharge is also soluble in organic bath, influence following for battery Ring performance.Therefore, how to improve the electric conductivity of material, and solve the problems of dissolution of discharge and recharge intermediate product, improve following for battery Ring performance, it is the research emphasis of sulfur-bearing positive electrode.

A kind of preparation method of lithium sulfur battery anode material is disclosed in patent application WO2012040934A1, including is passed through Ball milling mixes CNT, polyacrylonitrile copolymer and elemental sulfur, after vacuum drying, carries out under an inert atmosphere at heating Reason, is cooled to room temperature, that is, obtains positive electrode after heating.By this method in obtained composite, embedded poly- third Sulphur in alkene lonitrile copolymer is not complete enough, but also has some sulphur being not embedded in polyacrylonitrile copolymer and be present in again Condensation material, and due to the Volume Changes in the insulating properties and charge and discharge process of sulphur, the presence of these sulphur can reduce the electrification of material Performance is learned, so as to influence the performance of whole battery.

The content of the invention

The present invention provides a kind of preparation method of electrode composite material, comprises the following steps:Raw material mixes, and dries, obtains Mixture, the raw material comprise at least elemental sulfur and polyacrylonitrile, and the percentage by weight of the elemental sulfur is not less than 50%;Mixing Thing carries out first time heating under the first protective atmosphere, obtains compound, and the first time heats simple substance in atmosphere Sulphur is in saturation state;Compound carries out second under the second protective atmosphere and heated, and cooling, that is, obtains electrode composite wood Expect, elemental sulfur is in undersaturated condition in second of heating atmosphere.

In the preparation method of electrode composite material provided by the invention, elemental sulfur is excessive in reaction raw materials, meanwhile, In first time heat-treatment process, the elemental sulfur in reaction atmosphere is in saturation state so that more elemental sulfurs can be embedded in Into polyacrylonitrile, i.e., the elemental sulfur combined by chemical bond with polyacrylonitrile reaches complete, and unnecessary is not embedded into poly- third Elemental sulfur in alkene nitrile can be adsorbed around polyacrylonitrile, be present in and heated for the first time in atmosphere without with the first protection The air-flow of atmosphere is pulled away.The compound of gained carries out second of heating again after first time heats, second In secondary heat-treatment process, the elemental sulfur in reaction atmosphere is in undersaturated condition, and the concentration of elemental sulfur is lower in reaction atmosphere It is better, allow the elemental sulfur being not embedded into polyacrylonitrile evaporated in second of heat-treatment process after with the second protective atmosphere Air-flow is pulled away, and so as to preferably control the content of sulphur in gained composite, improves the chemical property of gained composite, And then improve the chemical property of whole lithium-sulfur cell.

In the preparation method of electrode composite material provided by the invention, it is preferred that gained is compound after heating for the first time When thing carries out second of heating under the second protective atmosphere, after first compound is divided into more than or equal to two parts, then will be each Part compound is respectively heated processing.

In the preparation method of electrode composite material provided by the invention, it is preferred that the air velocity of the second protective atmosphere is big In the air velocity of the first protective atmosphere.

In the preparation method of electrode composite material provided by the invention, it is preferred that raw material mixing includes ball milling, the ball milling The range of speeds be 300-500 revs/min, Ball-milling Time scope is 2-4 hours.

In the preparation method of electrode composite material provided by the invention, it is preferred that dry temperature range is 40-60 DEG C, Drying time scope is 2-4 hours.

In the preparation method of electrode composite material provided by the invention, it is preferred that the temperature range heated for the first time For 260-380 DEG C, the time range that the first time heats is 2-9 hours.

In the preparation method of electrode composite material provided by the invention, it is preferred that second of temperature range heated For 260-380 DEG C, second of time range heated is 1-3 hours.

In the preparation method of electrode composite material provided by the invention, it is preferred that raw material also includes in carbon nanometer tube material The percentage by weight of CNT is 0.5%-6%.

The present invention provides a kind of positive pole of battery, including electrode composite material, wherein, electrode composite material is by institute of the present invention The preparation method of the electrode composite material of offer is made.

The present invention also provides a kind of battery, including positive pole, negative pole and the electrolyte between positive pole and negative pole, described Positive pole includes plus plate current-collecting body and electrode composite material, wherein, electrode composite material is by electrode composite wood provided by the present invention The preparation method of material is made.

Brief description of the drawings

The invention will be further described with embodiment below in conjunction with the accompanying drawings.

Fig. 1 is in embodiment 1, at the DTG curves of compound obtained by after heating for the first time and second of heating The DTG curves of the electrode obtained combination electrode material after reason;

Fig. 2 is the battery of the battery and the gained of way of contrast 2 of the gained of embodiment 4, tests institute under the conditions of 0.2C respectively The circulation volume and cycle efficieny collection of illustrative plates obtained;

Fig. 3 is the battery of the battery and the gained of embodiment 8 of the gained of embodiment 4, tests institute under the conditions of 0.2C respectively The circulation volume and cycle efficieny collection of illustrative plates obtained;

Fig. 4 is the battery of the battery and the gained of embodiment 8 of the gained of embodiment 4, tests institute under the conditions of 0.5C respectively The circulation volume and cycle efficieny collection of illustrative plates obtained.

Embodiment

A kind of preparation method of electrode composite material, comprises the following steps:Raw material mixes, and dries, obtains mixture, described Raw material comprises at least elemental sulfur and polyacrylonitrile, and the percentage by weight of the elemental sulfur is not less than 50%;Mixture is protected first Protect and first time heating is carried out under atmosphere, obtain compound, wherein, heat elemental sulfur in atmosphere for the first time and be in saturation State;Compound carries out second under the second protective atmosphere and heated, and cooling, that is, obtains electrode composite material, wherein, the Elemental sulfur is in undersaturated condition in reheating processing atmosphere.

In the preparation method of electrode composite material provided by the invention, elemental sulfur is excessive in reaction raw materials, meanwhile, In first time heat-treatment process, the elemental sulfur in reaction atmosphere is in saturation state so that more elemental sulfurs can be embedded in Into polyacrylonitrile, i.e., the elemental sulfur combined by chemical bond with polyacrylonitrile reaches complete, and unnecessary is not embedded into poly- third Elemental sulfur in alkene nitrile can be then adsorbed around polyacrylonitrile, be present in and heated for the first time in atmosphere without being protected with first The air-flow of shield atmosphere is pulled away.The compound of gained carries out second of heating again after first time heats, the In reheating processing procedure, the elemental sulfur in reaction atmosphere is in undersaturated condition, and the concentration of elemental sulfur is got in reaction atmosphere It is low better, allow the elemental sulfur being not embedded into polyacrylonitrile evaporated in second of heat-treatment process after with the second protective atmosphere Air-flow be pulled away, so as to preferably control gained composite in sulphur content, improve gained composite electrochemistry Can, and then improve the chemical property of whole lithium-sulfur cell.

In a particular embodiment, heat elemental sulfur in atmosphere for the first time and be in saturation state, refer to first In secondary heat-treatment process, excessive elemental sulfur reacts with polyacrylonitrile in reaction raw materials, when reacting complete, is embedded into poly- The amount of elemental sulfur in acrylonitrile can reach a fixed value to be increased without being further continued for, and now, it is not embedded into polypropylene Unnecessary elemental sulfur in nitrile can then form sulphur steam and be present in reaction atmosphere, be adsorbed in around polyacrylonitrile, and adsorb Sulphur concentration around polyacrylonitrile is higher, will not be left with the air-flow of the first protective atmosphere.And heat atmosphere for the second time Middle elemental sulfur is in undersaturated condition, refers in second of heat-treatment process, and polyacrylonitrile week is adsorbed in reaction atmosphere The simple substance sulphur concentration enclosed reduces, and these elemental sulfurs will leave with the air-flow of the second protective atmosphere, compound what is finally obtained There would not be the elemental sulfur being not embedded into polyacrylonitrile to be present in around polyacrylonitrile again in electrode material.

In a preferred embodiment, first will be multiple when compound carries out second of heating under the second protective atmosphere After compound is divided into more than or equal to two parts, then processing will be respectively heated per a compound.By compound be divided into more than etc. After two parts of aliquot, the elemental sulfur in second of heating atmosphere can be made to reach undersaturated condition faster, so that The elemental sulfur that chemical bond is not formed with polyacrylonitrile can be taken out of with the air-flow of the second protective atmosphere after evaporation.

In a particular embodiment, the first protective atmosphere and the second protective atmosphere is gases used may be selected from argon gas, nitrogen One kind in the reducing gas that gas and argon gas mix with nitrogen.Also, gas used in the first protective atmosphere and the second protective atmosphere Body includes but are not limited to these gases.In a preferred embodiment, the air velocity of the second protective atmosphere is more than first and protected Protect the air velocity of atmosphere;It is more highly preferred to, the air velocity of the second protective atmosphere is the air velocity of the first protective atmosphere Twice.By controlling the air velocity of the first protective atmosphere and the second protective atmosphere, preferably ensure to heat gas for the first time Elemental sulfur in atmosphere is saturation state, and it is undersaturated condition to heat the elemental sulfur in atmosphere for the second time.

In a preferred embodiment, the elemental sulfur in raw material is S8, the average grain diameter of elemental sulfur is 80-120 mesh, poly- third The mean molecule quantity of alkene nitrile is 120000-180000;It is more highly preferred to, the average grain diameter of elemental sulfur is 100 mesh, polyacrylonitrile Mean molecule quantity is 150000.

In a preferred embodiment, raw material mixing includes ball milling, and the range of speeds of ball milling is 300-500 revs/min, ball milling Time range is 2-4 hours.It is furthermore preferred that the range of speeds of ball milling is 400 revs/min, Ball-milling Time scope is 3 hours.Protecting While card raw material is well mixed, the structure of polyacrylonitrile is not destroyed yet.Dispersant is used in mechanical milling process, makes raw material mixing more Add uniformly, dispersant is selected from the one kind being but not limited only in absolute ethyl alcohol, acetone or 1-METHYLPYRROLIDONE.It is furthermore preferred that ball Honed journey is carried out under an inert atmosphere, can preferably avoid that other side reactions occur in mechanical milling process, in order to avoid to material Have an impact, in the gases used reducing gas for including but is not limited to argon gas, nitrogen and nitrogen and being mixed with argon gas of inert atmosphere One kind.

In a preferred embodiment, dry temperature range is 40-60 DEG C, and drying time scope is 2-4 hours, more excellent Choosing, dry temperature range is 50 DEG C, and drying time scope is 3 hours, is preferably remained after removal ball milling in mixture Dispersant.It is more highly preferred to, drying process is carried out under vacuum.

In a preferred embodiment, the temperature range heated for the first time is 260-380 DEG C, the first time heating The time range of processing is 2-9 hours.It is more highly preferred to, the temperature heated for the first time is 320 DEG C, the first time heating The time of processing is 2-7 hours.While ensureing that raw material fully reacts, also avoid elemental sulfur from quickly volatilizing, make excessive list Matter sulphur can be bonded by chemical combination with polyacrylonitrile and closed as far as possible.

In a preferred embodiment, second of temperature range heated is 260-380 DEG C, second of heating The time range of processing is 1-3 hours.It is more highly preferred to, second of temperature heated is 320 DEG C, second of heating The time of processing is 2 hours.Make to fail to be embedded into the elemental sulfur in polyacrylonitrile in whole atmosphere, it is heat-treated at second Evaporated in journey, and as the air-flow of the second protective atmosphere is pulled away, while the sulphur for also ensureing to have been combined with polyacrylonitrile will not Abjection.

In a particular embodiment, the temperature that second of temperature heated heats with first time can be complete It is identical, it is possibility to have institute is different.

In a preferred embodiment, the preparation method of electrode composite material specifically comprises the following steps:By weight percent Than the polyacrylonitrile for being 120000-180000 with mean molecule quantity not less than the elemental sulfur that 50%, average grain diameter is 80-120 mesh The ball milling 2-4h in ball mill, the rotating speed of ball mill is 300-500 revs/min, and dispersant used is absolute ethyl alcohol in mechanical milling process, 2-4h is dried obtained by ball milling under 40-60 DEG C of vacuum condition, obtains mixture;Gained mixture under the first protective atmosphere First time heating is carried out at 260-380 DEG C, after heating 2-9h, obtains compound, wherein, heat gas for the first time Elemental sulfur is in saturation state in atmosphere;Gained compound carries out second at 260-380 DEG C under the second protective atmosphere and heated Processing, after heating 1-3h, natural cooling, that is, electrode composite material is obtained, wherein, simple substance in second of heating atmosphere Sulphur is in undersaturated condition.

In a preferred embodiment, raw material includes elemental sulfur, polyacrylonitrile and carbon-based material, the general general character of carbon-based material The ratio surface that feature is is very big, has stronger adsorption function, while also has excellent electric conductivity, is well suited as conduction and adds Add material.Carbon-based material may be selected from least one of section's qin carbon black (KB), acetylene black, activated carbon, CNT, graphene. In preferred embodiment, raw material includes elemental sulfur, polyacrylonitrile and CNT, and the addition of CNT can improve The electric conductivity of sulfenyl composite, meanwhile, the particle of sulfenyl composite can be connected, to electrode in removal lithium embedded process In Volume Changes stable support is provided, improve the charge-discharge performance of sulfenyl composite active material.It is furthermore preferred that carbon nanometer Manage as multi-walled carbon nanotube, the percentage by weight of CNT is 0.5%-6%.

In preferred embodiment, the preparation method of electrode composite material, specifically comprise the following steps:By weight hundred Divide than not less than the elemental sulfur that 50%, average grain diameter is 80-120 mesh, mean molecule quantity is 120000-180000 polyacrylonitrile With percentage by weight be 0.5%-6% multi-walled carbon nanotube in ball mill ball milling 2-4h, the rotating speed of ball mill is 300-500 Rev/min, dispersant used is absolute ethyl alcohol in mechanical milling process, and 2-4h is dried under 40-60 DEG C of vacuum condition obtained by ball milling, is obtained To mixture;Obtained mixture carries out first time heating under the first protective atmosphere at 260-380 DEG C, heats After 2-9h, compound is obtained, wherein, heat elemental sulfur in atmosphere for the first time and be in saturation state;Obtained compound exists Second is carried out at 260-380 DEG C to heat, after heating 1-3h, natural cooling, that is, obtain under second protective atmosphere Electrode composite material, wherein, elemental sulfur is in undersaturated condition in second of heating atmosphere.

Electrode composite material made from preparation method recited above can be used as battery positive electrode active material, electrode composite wood Material forms a kind of positive pole of battery in the lump with plus plate current-collecting body.

A kind of battery, including positive pole, negative pole and the electrolyte between positive pole and negative pole.

Positive pole includes plus plate current-collecting body and positive active material.Positive active material contains above-mentioned electrode composite material, Electrode composite material accounts for the 50-90% of positive active material gross weight, wherein, positive active material also includes electrically conductive material And binding agent.In preferred embodiment, the weight proportion of the electrode composite material in positive active material is 80%.

Electrically conductive material is selected from conducting polymer, activated carbon, graphene, carbon black, carbon fiber, metallic fiber, metal powder One or more in end and sheet metal.In preferably embodiment, electrically conductive material selects section's qin carbon black (KB) Or acetylene black.

Binding agent is selected from polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimides, polyester, polyethers, fluorination Polymer, poly- divinyl polyethylene glycol, polyethyleneglycol diacrylate, one kind in glycol dimethacrylates or The mixture and derivative of above-mentioned polymer.In preferably embodiment, binding agent includes Kynoar (PVDF).Bond Agent accounts for the 1-30% of positive active material gross weight.

During preparing anode sizing agent, as dispersant organic solvent be selected from but be not limited only to absolute ethyl alcohol, acetone or One kind in 1-METHYLPYRROLIDONE.

Plus plate current-collecting body is selected from the one kind being but not limited only in nickel foam, aluminium foil or stainless (steel) wire.As preferred side Case, plus plate current-collecting body are nickel foam.

Negative pole is lithium metal or lithium alloy.

Electrolyte comprises at least electrolyte lithium salt and mixed organic solvents.

Electrolyte lithium salt can include but are not limited to lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), perchloric acid Lithium (LiClO4), trifluoromethyl sulfonic acid lithium (LiCF3SO3), bis trifluoromethyl sulfimide lithium (LiN (CF3SO2)2).In electrolyte Addition lithium salts can effectively increase the ionic conductance of electrolyte.

The solvent of electrolyte can be common organic solvent, such as dimethoxy-ethane (DME), ethene carbonic ether (EC), Carbovinate fat (DEC), propylene carbonate (PC), 1,3- dioxolane (DIOX), various ether, glyme are interior Ester, sulfone, sulfolane or more mixture.For example use 1,3- dioxolanes (DIOX);It can also be polymer, such as PVDF, gather Vinylidene-polymethyl methacrylate copolymer (PVDF-PMMA), Kynoar-hexafluoropropylene copolymer (PVDF- HFP), polyethylene glycol borate polymer (PEG-borate esters).

In a particular embodiment, electrolyte is to contain lithium hexafluoro phosphate (LiPF6) ethylene carbonate (EC), diformazan The mixed solution of base carbonic ester (DMC) and diethyl carbonate (DEC).Electrolyte with the prominent form of gel in the battery, Be advantageous to prevent the seepage of potential battery electrolyte, avoid polluting environment, while also improve the security of battery.

The battery that the embodiment of the present invention provides, if needing to use barrier film in battery structure, barrier film is organic Porous material or glass fiber material, the aperture of barrier film are 0.001-100 microns, porosity 20-95%.

In a particular embodiment, electrode composite material, electrically conductive material, binding agent are mixed, added organic molten Anode sizing agent is made as dispersant in agent.Using it is any can be provided in the whole surface of plus plate current-collecting body it is substantially homogeneous The method of coat, obtained anode active material slurry is deposited on the surface of plus plate current-collecting body.For example, can be by scraping Knife rubbing method (doctor blade), coiling pull bar method (wired draw rod) method, silk-screen printing or other method.By normal Evaporation under pressure or low pressure and environment temperature or high temperature, can will remove solvent in anode active material slurry layer, molten The speed that agent removes is preferably to keep being basically unchanged along pulp surface.Then by obtained positive pole and negative pole, electrolyte, barrier film CR2032 button cells are assembled into together.

Below by embodiment, the present invention is further described.

Embodiment 1

By the S that 8.57g average grain diameters are 100 mesh8Pass through ball milling with 1.43g mean molecule quantities for 150000 polyacrylonitrile 3h, rotational speed of ball-mill 400rpm are mixed, dispersant is absolute ethyl alcohol, and 3h is dried under 50 DEG C of vacuum conditions obtained by ball milling, is obtained Mixture, mixture under nitrogen protection, heat 7h at 320 DEG C, obtain compound, single in the heating atmosphere Matter sulphur is in saturation state;Compound point is placed in several small crucibles again, the compound in each crucible is 1g, each earthenware Compound in crucible under nitrogen protection, heats 2h, in the heating atmosphere, elemental sulfur is at 320 DEG C respectively Undersaturated condition, natural cooling, that is, obtain electrode composite material S/DPAN.

Fig. 1 is gained electricity after compound obtained by after heating for the first time and second of heating in embodiment 1 The DTG curves of pole combination electrode material.As can be seen from the figure:After heating for the first time in the DTG curves of gained compound There are two peaks, wherein, peak corresponding to 210 DEG C of places is the melting peak of elemental sulfur, and another peak is then the starting of the compound Decomposition peak;And there was only a peak in the DTG curves of gained composite after heating for the second time, wherein, the melting of elemental sulfur Peak disappears, meanwhile, the starting decomposition peak of composite is moved at higher temperature.Illustrate after second is heated, No longer containing the elemental sulfur being not embedded into PAN in gained composite, meanwhile, the thermal stability of composite is also carried It is high.

Embodiment 2

By the S that 8.57g average grain diameters are 105 mesh8Pass through ball milling with 1.43g mean molecule quantities for 140000 polyacrylonitrile 3h, rotational speed of ball-mill 400rpm are mixed, dispersant is absolute ethyl alcohol, and 3h is dried under 50 DEG C of vacuum conditions obtained by ball milling, is obtained Mixture, mixture under nitrogen protection, heat 3h at 320 DEG C, obtain compound, single in the heating atmosphere Matter sulphur is in saturation state;Compound point is placed in several small crucibles again, the compound in each crucible is 1g, each earthenware Compound in crucible under nitrogen protection, heats 3h, in the heating atmosphere, elemental sulfur is at 300 DEG C respectively Undersaturated condition, natural cooling, that is, obtain electrode composite material S/DPAN.

Embodiment 3

Electrode composite material S/DPAN, 0.02g binding agent PVDF, 0.02g obtained by 0.16g embodiments 1 is electric Proton conduction KB is mixed, and adds 1-METHYLPYRROLIDONE as solvent, obtained slurry is coated by scraper for coating technology In the foamed nickel current collector of 800 μ m-thicks, it is dried in vacuo 12 hours at 60 DEG C, then by obtained material in tablet press machine lower sheeting Positive plate is made.

Embodiment 4

Gained positive plate is as positive pole using in embodiment 3, and using lithium metal as negative pole, porous polypropylene is barrier film, 1mol/ L lithium hexafluoro phosphates (LiPF6) ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) (body Product ratio 1:1:1) mixed solution is electrolyte, CR2032 button cells is assembled into the glove box full of argon gas, at room temperature Carry out battery performance test.

Embodiment 5

By the S that 8.57g average grain diameters are 100 mesh8, 1.43g mean molecule quantities be 150000 polyacrylonitrile and 0.5g it is more Wall carbon nano tube is absolute ethyl alcohol by ball milling mixing 3h, rotational speed of ball-mill 400rpm, dispersant, and ball milling gained is in 50 DEG C of vacuum Under the conditions of dry 3h, obtain mixture, mixture under nitrogen protection, heats 7h at 320 DEG C, obtains compound, should Heat in atmosphere, elemental sulfur is in saturation state;Compound point is placed in several small crucibles again, in each crucible Compound is 1g, and the compound in each crucible under nitrogen protection, heats 2h, the heating at 320 DEG C respectively In atmosphere, elemental sulfur is in undersaturated condition, natural cooling, that is, obtains electrode composite material S/DPAN/CNT.

Embodiment 6

By the S that 8.57g average grain diameters are 90 mesh8, 1.43g mean molecule quantities be 155000 polyacrylonitrile and the more walls of 0.5g CNT is absolute ethyl alcohol by ball milling mixing 3h, rotational speed of ball-mill 400rpm, dispersant, and ball milling gained is in 50 DEG C of vacuum bars 3h is dried under part, obtains mixture, mixture under nitrogen protection, heats 3h at 300 DEG C, obtains compound, should add In heat-treating atmosphere, elemental sulfur is in saturation state;Compound point is placed in several small crucibles again, answering in each crucible Compound is 1g, and the compound in each crucible under nitrogen protection, heats 2h, the heating gas at 320 DEG C respectively In atmosphere, elemental sulfur is in undersaturated condition, natural cooling, that is, obtains electrode composite material S/DPAN/CNT.

Embodiment 7

By electrode composite material S/DPAN/CNT, 0.02g binding agent PVDF obtained by 0.16g embodiments 5, 0.02g electrically conductive materials acetylene black mixes, and 1-METHYLPYRROLIDONE is added as solvent, by obtained slurry by scraping cutter painting In foamed nickel current collector of the cloth technology coated in 800 μ m-thicks, dual coating, it is dried in vacuo 12 hours at 60 DEG C, then will system Positive plate is made in tablet press machine lower sheeting in the material obtained.

Embodiment 8

Gained positive plate is as positive pole using in embodiment 7, and using lithium metal as negative pole, porous polypropylene is barrier film, 1mol/ L lithium hexafluoro phosphates (LiPF6) ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) (body Product ratio 1:1:1) mixed solution is electrolyte, CR2032 button cells is assembled into the glove box full of argon gas, at room temperature Carry out battery performance test.

Way of contrast 1

Gained compound, 0.02g binding agent PVDF, 0.02g electrically conductive materials KB in 0.16g embodiments 1 are mixed, 1-METHYLPYRROLIDONE is added as solvent, obtained slurry is passed through into nickel foam of the scraper for coating technology coated in 800 μ m-thicks On collector, it is dried in vacuo at 60 DEG C 12 hours, positive plate then is made in tablet press machine lower sheeting in obtained material.

Way of contrast 2

Gained positive plate is as positive pole using in way of contrast 1, and using lithium metal as negative pole, porous polypropylene is barrier film, 1mol/ L lithium hexafluoro phosphates (LiPF6) ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) (body Product ratio 1:1:1) mixed solution is electrolyte, CR2032 button cells is assembled into the glove box full of argon gas, at room temperature Carry out battery performance test.

Specifically the performance test mode of battery is:At room temperature by obtained battery standing for a period of time after, to battery carry out Constant current charge-discharge, charge-discharge magnification are respectively 0.2C and 0.5C (1C=1672mAh g-1), voltage range 1-3V.Based on just S content calculates the specific capacity of battery and current density in the material of pole.

Fig. 2 is the battery of the battery and the gained of way of contrast 2 of the gained of embodiment 4, tests institute under the conditions of 0.2C respectively The circulation volume and cycle efficieny collection of illustrative plates obtained.As can be seen from the figure:The cycle efficieny of both materials is all very good, still After heating second gained composite as positive electrode assemble obtained by battery capacity be substantially higher in merely through Gained compound assembles the capacity of gained battery as positive electrode after heating for the first time.

Fig. 3 is the battery of the battery and the gained of embodiment 8 of the gained of embodiment 4, tests institute under the conditions of 0.2C respectively The circulation volume and cycle efficieny collection of illustrative plates obtained.As can be seen from the figure:The cycle efficieny of battery obtained by both embodiments It is all very good, but the capacity of the battery of the gained of embodiment 6 is higher, cycle performance is also more preferable.

Fig. 4 is the battery of the battery and the gained of embodiment 8 of the gained of embodiment 4, tests institute under the conditions of 0.5C respectively The circulation volume and cycle efficieny collection of illustrative plates obtained.As can be seen from the figure:The cycle efficieny of both materials is all very good, still The cycle efficieny of battery is all very good obtained by both embodiments, but the capacity of the battery of the gained of embodiment 6 is higher, follows Ring performance is also more preferable, and its performance difference becomes apparent relative under the conditions of 0.2C.

Although inventor has done more detailed elaboration and enumerated to technical scheme, it will be appreciated that for For those skilled in the art, above-described embodiment is modified and/or the flexible or equivalent alternative solution of use is obvious , can not all depart from the essence of spirit of the present invention, the term occurred in the present invention be used for elaboration to technical solution of the present invention and Understand, can not be construed as limiting the invention.

Claims (9)

  1. A kind of 1. preparation method of electrode composite material, it is characterised in that:The preparation method comprises the following steps:
    Raw material mixes, and dries, obtains mixture, the raw material includes elemental sulfur, polyacrylonitrile and CNT, the elemental sulfur Percentage by weight be not less than 50%;
    The mixture carries out first time heating under the first protective atmosphere, obtains compound, at the first time heating Elemental sulfur is in saturation state in qi-regulating atmosphere;
    The compound carries out second under the second protective atmosphere and heated, and cooling, that is, obtains electrode composite material, described Second, which heats elemental sulfur in atmosphere, be in undersaturated condition, and the air velocity of second protective atmosphere is more than described the The air velocity of one protective atmosphere.
  2. 2. according to the preparation method described in claim 1, it is characterised in that:The compound is carried out under the second protective atmosphere During second of heating, after the compound is divided into more than or equal to two parts, place will be respectively heated per a compound Reason.
  3. 3. according to the preparation method described in claim 1, it is characterised in that:The raw material mixing includes ball milling, the ball milling The range of speeds be 300-500 revs/min, the time range of the ball milling is 2-4 hours.
  4. 4. according to the preparation method described in claim 1, it is characterised in that:The temperature range of the drying is 40-60 DEG C, institute It is 2-4 hours to state dry time range.
  5. 5. according to the preparation method described in claim 1, it is characterised in that:The temperature range that first time heats is 260-380 DEG C, the time range that the first time heats is 2-9 hours.
  6. 6. according to the preparation method described in claim 1, it is characterised in that:Described second temperature range heated is 260-380 DEG C, second of time range heated is 1-3 hours.
  7. 7. according to the preparation method described in claim 1, it is characterised in that:The percentage by weight of the CNT is 0.5%-6%.
  8. 8. a kind of positive pole of battery, including electrode composite material, the electrode composite material is by any one in claim 1-7 The preparation method of the electrode composite material is made.
  9. 9. a kind of battery, including positive pole, negative pole and the electrolyte between positive pole and negative pole, the positive pole include positive pole collection Fluid and electrode composite material, electrode composite material electrode composite material as described in any one in claim 1-7 Preparation method is made.
CN201711020262.4A 2012-10-26 2012-10-26 The preparation method of electrode composite material, positive pole, the battery with the positive pole CN107768654A (en)

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US20170179468A1 (en) * 2014-06-06 2017-06-22 Robert Bosch Gmbh Polymer electrolyte for a lithium sulfur cell
WO2016019544A1 (en) * 2014-08-07 2016-02-11 Robert Bosch Gmbh Sulfur-polyacrylonitrile composite, preparation and use thereof
CN104282892B (en) * 2014-10-09 2016-09-28 江苏华东锂电技术研究院有限公司 The preparation method of sulfur-based positive electrode material
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