CN106328883A - Lithium thionyl chloride battery positive electrode and preparation method thereof - Google Patents

Lithium thionyl chloride battery positive electrode and preparation method thereof Download PDF

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Publication number
CN106328883A
CN106328883A CN201610924024.5A CN201610924024A CN106328883A CN 106328883 A CN106328883 A CN 106328883A CN 201610924024 A CN201610924024 A CN 201610924024A CN 106328883 A CN106328883 A CN 106328883A
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CN
China
Prior art keywords
acetylene black
positive electrode
cnt
thionyl chloride
lithium thionyl
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Pending
Application number
CN201610924024.5A
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Chinese (zh)
Inventor
谭思平
魏俊华
陈铤
王庆杰
赵洪楷
万伟华
钱顺友
蔡波
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Guizhou Meiling Power Supply Co Ltd
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Guizhou Meiling Power Supply Co Ltd
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Priority to CN201610924024.5A priority Critical patent/CN106328883A/en
Publication of CN106328883A publication Critical patent/CN106328883A/en
Pending legal-status Critical Current

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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 discloses a lithium thionyl chloride battery positive electrode and a preparation method thereof. The lithium thionyl chloride battery positive electrode contains a conductive material represented by acetylene black and carbon nano tube, wherein the weight parts of the acetylene black and the carbon nano tube are as follows: 70-90 of acetylene black and 25-5 of carbon nano tube. A carbon film of a composite positive electrode is prepared by mixing the acetylene black with the liquid phase of the carbon nano tube, and the prepared carbon positive electrode has good conductivity, while the polarization of a carbon electrode is reduced due to increase of conductivity, thus improving the electrical properties of the electrode; the voltage increasing amount of the battery reaches 20mV, and the capacity increase amount reaches 1.3Ah, and therefore, the battery positive electrode prepared according to a liquid phase mixing method promotes the working voltage and capacity of the battery.

Description

A kind of positive electrode of lithium thionyl chloride battery and preparation method thereof
Technical field
The present invention relates to cell art, particularly relate to a kind of positive electrode of lithium thionyl chloride battery, further relate to a kind of lithium The preparation method of thionyl chloride battery positive pole.
Background technology
Lithium thionyl chloride cell be actual application one-shot battery series in running voltage the highest (3.6V) and actual output A kind of battery (specific energy 590W h/Kg) that specific energy is the highest, and be widely used in civilian and military aerospace field.Due to The conductive materials such as the CNT used by anode have hydrophobic characteristic, thus cause the materials such as CNT in water Being difficult to be disperseed, the powder that acetylene black and CNT are obtained by mechanical mixture is uneven, thus causes the electrode pole prepared Change big.As it is shown in figure 1, when the mass fraction of CNT is 25%, the carbon film intensity difference prepared by the method for mechanical mixture, Hole is many, shows that mechanical mixture is to the acetylene black of hydrophobicity difference, the processing method weak effect of the material such as CNT.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of positive electrode of lithium thionyl chloride battery and preparation method thereof, preparation Go out that content of carbon nanotubes is higher, mixability positive electrode evenly, promote the electrical property of battery.
The technical scheme that the present invention takes is: a kind of positive electrode of lithium thionyl chloride battery, comprises acetylene black and CNT, second Acetylene black and the weight part ratio in the electrodes of CNT: acetylene black 70～90, CNT 25～5.
Above-mentioned anode also comprises ptfe emulsion, ptfe emulsion and acetylene black and the weight of CNT Amount part ratio is: ptfe emulsion 5, acetylene black 70～90, CNT 25～5.
A kind of preparation method of positive electrode of lithium thionyl chloride battery, the method comprises the following steps:
(1) mechanical ball milling: respectively CNT and acetylene black powder body are carried out ball-milling treatment 1h by the method for mechanical ball milling, to obtain Obtain the powder that granularity is consistent；
(2) ultrasonic disperse: two kinds of powder body step 1) obtained are separately added in ionized water, adds ptfe emulsion, and Carry out the ultrasonic disperse of 30min；
(3) ultrasonic agitation: by step 2) two kinds of dispersion liquids mixing of obtaining, and carry out the ultrasonic agitation of 30min；
(4) sucking filtration: the mixed liquor of step 3) is carried out sucking filtration, the filtering residue collected obtains powder after drying, and 70 DEG C are dried 24h；
(5) molding: add ethanol in the powder that step 4) obtains and with hot calender, this mixture be pressed into carbon film, compacting Nickel screen collector makes electrode.
Beneficial effects of the present invention: compared with prior art, effect of the present invention is as follows:
(1) positive electrode using li quid mixing method to prepare overcomes the original hydrophobicity of carbon nano-tube material, has dispersion all The advantage that even CNT compound quantity is big, and improve the output voltage of battery；
(2) the carbon positive pole prepared has good electric conductivity, and the increase of electric conductivity reduces the polarization on carbon electrode, uses the party Electrode voltage and capacity prepared by method are all obviously improved；
(3) the carbon film intensity that prepared by li quid mixing method is high, it is easier to be processed into electrode slice, and Preparation equipment requires to reduce, and is prepared as This reduction.
Accompanying drawing explanation
Fig. 1 is the carbon film of the carbon nanotube mass mark 25% that the li quid mixing method of the present invention is prepared with mechanical mix techniques Contrast photo；
Fig. 2 is putting of the carbon film of the carbon nanotube mass mark 10% that the li quid mixing method of the present invention is prepared with mechanical mix techniques Electricity curve comparison.
Detailed description of the invention
Below in conjunction with the accompanying drawings and the present invention is described further by specific embodiment.
Embodiment 1: a kind of positive electrode of lithium thionyl chloride battery, comprises acetylene black, CNT and ptfe emulsion, should The preparation method of electrode comprises the following steps:
(1) mechanical ball milling: acetylene black 90g and CNT 5g are respectively put in ball grinder, uses the method for mechanical ball milling to divide The other ball-milling treatment that the two is carried out 1h；
(2) ultrasonic disperse: two kinds of powder body step 1) obtained are separately added in the deionized water of 900ml and 100ml, then distinguish Add the ptfe emulsion of 4.5g and 0.5g, be placed in supersonic cleaning machine and carry out ultrasonic disperse, supersound process 30min, make Politef and powder are dispersed in water；
(3) ultrasonic agitation: by step 2) two kinds of dispersion liquids mixing of obtaining, and ultrasonic agitation 30min under 80W power；
(4) sucking filtration: the mixed liquor of step 3) is carried out sucking filtration, the filtering residue collected is placed in baking oven and dries 24h with 70 DEG C, collects and dry Powder is obtained after Gan；
(5) molding: add in the powder that step 4) obtains ethanol and with hot calender this mixture is pressed into 30mm × The carbon film of 40mm, is compressed on nickel screen collector and makes carbon positive pole；
Carbon film positive pole is assembled into together with cathode of lithium pole plate group, loads square rustless steel battery container, inject 1.5M LiAlCl4/SOCl2Electrolyte, carries out welded seal to liquid injection hole.
The electric discharge result of embodiment 1 is shown, uses the electrode phase of the electrode prepared of li quid mixing method and mechanical mixture Ratio, voltage improves 20mV, and capacity improves 1.3Ah/g.
Embodiment 2: a kind of positive electrode of lithium thionyl chloride battery, comprises acetylene black, CNT and ptfe emulsion, should The preparation method of electrode comprises the following steps:
(1) mechanical ball milling: acetylene black 80g and CNT 15g are respectively put in ball grinder, uses the method for mechanical ball milling to divide The other ball-milling treatment that the two is carried out 1h；
(2) ultrasonic disperse: two kinds of powder body step 1) obtained are separately added in the deionized water of 800ml and 200ml, then distinguish Add the ptfe emulsion of 4g and 1g, be placed in supersonic cleaning machine and carry out ultrasonic disperse, supersound process 30min, make poly-four Fluorothene and powder are dispersed in water；
(3) ultrasonic agitation: by step 2) two kinds of dispersion liquids mixing of obtaining, and ultrasonic agitation 30min under 80W power；
(4) sucking filtration: the mixed liquor of step 3) is carried out sucking filtration, the filtering residue collected is placed in baking oven and dries 24h with 70 DEG C, collects and dry Powder is obtained after Gan；
(5) molding: add in the powder that step 4) obtains ethanol and with hot calender this mixture is pressed into 30mm × The carbon film of 40mm, is compressed on nickel screen collector and makes carbon positive pole；
Carbon film positive pole is assembled into together with cathode of lithium pole plate group, loads square rustless steel battery container, inject 1.5M LiAlCl4/SOCl2Electrolyte, carries out welded seal to liquid injection hole.
To carrying out discharge test in embodiment 2, test shows, the electrode using li quid mixing method to prepare mixes with machinery The electrode closed is compared, and voltage improves 22mV, and capacity improves 1.33Ah/g.
Embodiment 3: a kind of positive electrode of lithium thionyl chloride battery, comprises acetylene black, CNT and ptfe emulsion, should The preparation method of electrode comprises the following steps:
(1) mechanical ball milling: acetylene black 70g and CNT 25g are respectively put in ball grinder, uses the method for mechanical ball milling to divide The other ball-milling treatment that the two is carried out 1h；
(2) ultrasonic disperse: two kinds of powder body step 1) obtained are separately added in the deionized water of 700ml and 300ml, then distinguish Add the ptfe emulsion of 3.5g and 1.5g, be placed in supersonic cleaning machine and carry out ultrasonic disperse, supersound process 30min, make Politef and powder are dispersed in water；
(3) ultrasonic agitation: by step 2) two kinds of dispersion liquids mixing of obtaining, and ultrasonic agitation 30min under 80W power；
(4) sucking filtration: the mixed liquor of step 3) is carried out sucking filtration, the filtering residue collected is placed in baking oven and dries 24h with 70 DEG C, collects and dry Powder is obtained after Gan；
(5) molding: add in the powder that step 4) obtains ethanol and with hot calender this mixture is pressed into 30mm × The carbon film of 40mm, is compressed on nickel screen collector and makes carbon positive pole；
Carbon film positive pole is assembled into together with cathode of lithium pole plate group, loads square rustless steel battery container, inject 1.5M LiAlCl4/SOCl2Electrolyte, carries out welded seal to liquid injection hole.
To carrying out discharge test in embodiment 3, test shows, the electrode using li quid mixing method to prepare mixes with machinery The electrode closed is compared, and voltage improves 26mV, and capacity improves 1.42Ah/g.
The above, the only detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, and any Those familiar with the art, in the technical scope that the invention discloses, can readily occur in change or replace, should contain Covering within protection scope of the present invention, therefore, protection scope of the present invention should be as the criterion with described scope of the claims.

Claims (3)

1. a positive electrode of lithium thionyl chloride battery, it is characterised in that: comprise acetylene black and CNT, acetylene black and CNT Weight part ratio in the electrodes: acetylene black 70～90, CNT 25～5.
A kind of positive electrode of lithium thionyl chloride battery the most according to claim 1, it is characterised in that: anode also comprises poly-four Fluorothene emulsion, ptfe emulsion with the weight part ratio of acetylene black and CNT is: ptfe emulsion 5, acetylene Black 70～90, CNT 25～5.
3. the preparation method of a kind of positive electrode of lithium thionyl chloride battery as described in one of claim 1-2, it is characterised in that: the party Method comprises the following steps:
(1) mechanical ball milling: respectively CNT and acetylene black powder body are carried out ball-milling treatment 1h by the method for mechanical ball milling；
(2) ultrasonic disperse: two kinds of powder body step 1) obtained are separately added in ionized water, are also separately added into politef Emulsion, and carry out the ultrasonic disperse of 30min；
(3) ultrasonic agitation: by step 2) two kinds of dispersion liquids mixing of obtaining, and carry out the ultrasonic agitation of 30min；
(4) sucking filtration: the mixed liquor of step 3) is carried out sucking filtration, the filtering residue collected obtains powder after drying, and 70 DEG C are dried 24h；
(5) molding: add ethanol in the powder that step 4) obtains and with hot calender, this mixture be pressed into carbon film, pressure System makes electrode on nickel screen collector.
CN201610924024.5A 2016-10-24 2016-10-24 Lithium thionyl chloride battery positive electrode and preparation method thereof Pending CN106328883A (en)

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Application Number Priority Date Filing Date Title
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CN110690450A (en) * 2019-10-24 2020-01-14 惠州亿纬锂能股份有限公司 Carbon electrode and forming method and application thereof

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Publication number Priority date Publication date Assignee Title
CN110690450A (en) * 2019-10-24 2020-01-14 惠州亿纬锂能股份有限公司 Carbon electrode and forming method and application thereof
CN110690450B (en) * 2019-10-24 2023-03-31 惠州亿纬锂能股份有限公司 Carbon electrode and forming method and application thereof

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Application publication date: 20170111