CN102208675B - Lithium/thionyl dichloride battery - Google Patents
Lithium/thionyl dichloride battery Download PDFInfo
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- CN102208675B CN102208675B CN2011101105350A CN201110110535A CN102208675B CN 102208675 B CN102208675 B CN 102208675B CN 2011101105350 A CN2011101105350 A CN 2011101105350A CN 201110110535 A CN201110110535 A CN 201110110535A CN 102208675 B CN102208675 B CN 102208675B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a lithium/thionyl dichloride battery, which is characterized in that lithium is taken as an anode, carbon is taken as a cathode carrier, a thionyl dichloride solution of anhydrous lithium aluminum tetrachloride is taken as an electrolyte, and an active material of the battery contains calcium metal halides. The lithium/thionyl dichloride battery can improve voltage hysteretic properties and be used under the condition of intermediate-rate and high-rate discharge at a low temperature.
Description
Technical field
The present invention relates to the technical field of battery, be meant a kind of lithium/thinly chloride battery especially.
Background technology
Lithium/thinly chloride (Li/SOCl
2) battery be a kind of be anode with the lithium, carbon is made cathode carrier, the thionyl chloride (SOCl of anhydrous tetrachloro-lithium aluminate
2) solution makes the lithium battery of electrolyte.Characteristics such as lithium/thinly chloride battery has that specific energy height, specific power are big, discharging voltage balance, storage life are long all are widely used in military and civilian industry such as Aero-Space, underawater ordnance, navigator, geological prospecting, instrument and meter.Lithium/thinly chloride battery is specific energy and the highest a kind of battery of specific power in the current battery field.
The subject matter that lithium/thinly chloride battery exists is voltage delay and safety problem, and wherein the voltage delay problem is having a strong impact on the performance of the excellent properties of lithium/thinly chloride battery, is seriously restricting the application of lithium/thinly chloride battery.And cause the main cause of lithium/thinly chloride battery voltage delay, then be that product lithium chloride (LiCl) in the cell reaction process forms the fine and close passivating film of one deck on attached to lithium anodes, thereby stop cell reaction to be proceeded.Battery long term storage or under hot conditions, use, the passivating film of this densification constantly thickens, and its voltage delay phenomenon is even more serious.
The manufacture method of existing lithium/thinly chloride battery negative electrode; It is general that all to adopt by certain material proportion be that 60% ptfe emulsion fully stirs with deionized water, absolute ethyl alcohol, acetylene black, concentration; Process " paste " of lithium/thinly chloride battery negative electrode, and then " paste " dewatered and heat fibrillatable and be processed into required negative electrode pole piece.
The preparation method of existing lithium/thinly chloride battery electrolyte generally all adopts tetrachloro-lithium aluminate (LiAlCl
4) be dissolved in the thionyl chloride by normal concentration, add the lithium paper tinsel and stir; Adopt the reflux mode to dewater again and make required electrolyte.
According to the lithium/thinly chloride battery of above-mentioned explained hereafter, there are voltage delay and safety problem.In order to eliminate lithium/thinly chloride battery voltage delay phenomenon, adopt mostly and improve the afflux form of negative electrode and anode, or improve the impurity content and the molar concentration of electrolyte, to reduce the internal resistance of cell; Add electronic components at inside battery or outside, make battery be in the weak discharge state, with the formation of reduction passivating film; In negative electrode and electrolyte, add modes such as metal phthalocyanine compound or sulfide, to improve the voltage delay performance.Some can improve some performance of lithium/thinly chloride battery to a certain extent said method, but some then its capacity with " sacrifice " lithium/thinly chloride battery be cost, weakened the other performance of lithium/thinly chloride battery.
Summary of the invention
Technical problem to be solved by this invention is: provides a kind of and can improve the voltage delay performance, and the lithium/thinly chloride battery that can under low temperature and middle and high multiplying power discharging condition, use.
For addressing the above problem, the technical scheme that the present invention adopts is: a kind of lithium/thinly chloride battery is an anode with the lithium, and carbon is made cathode carrier, and the thionyl chloride solution of anhydrous tetrachloro-lithium aluminate is made electrolyte, contains the calcium metal halide in the active material of battery.
Described calcium metal halide is a calcium chloride.
Described calcium metal halide is mixed in the cathode material of lithium/thinly chloride battery, and calcium metal halide shared mass ratio in the cathode material of lithium/thinly chloride battery is 0.01 ~ 0.06.
Described calcium metal halide is mixed in the electrolyte material of lithium/thinly chloride battery, and the calcium metal halide reaches capacity in the electrolyte material of lithium/thinly chloride battery.
Described calcium metal halide is mixed in the electrolyte material of the cathode material of lithium/thinly chloride battery and lithium/thinly chloride battery; And calcium metal halide shared mass ratio in the cathode material of lithium/thinly chloride battery is 0.01 ~ 0.06, and the calcium metal halide reaches capacity in the electrolyte material of lithium/thinly chloride battery.
The invention has the beneficial effects as follows: above-mentioned lithium/thinly chloride battery is owing to contain the calcium metal halide in the cell active materials, and the adding of this calcium metal halide is improved the performance of lithium/thinly chloride battery greatly.This is because calcium has preferably open circuit voltage, excellent characteristic such as discharge capacity and anti-preferably thionyl chloride passivation preferably in thionyl chloride.Therefore; Because the adding of calcium metal halide; Effect through cathode active material thionyl chloride in the lithium/thinly chloride battery; Suppress the formation on lithium metal anode surface " passivating film ", made lithium/thinly chloride battery obtain good discharge voltage and discharge capacity, significantly improved the voltage delay phenomenon of lithium/thinly chloride battery.
Embodiment
Through specific embodiment a kind of lithium/thinly chloride battery of the present invention is done further to describe in detail below.
Embodiment 1
A kind of lithium/thinly chloride battery; With the lithium is anode; Carbon is made cathode carrier, and the thionyl chloride solution of anhydrous tetrachloro-lithium aluminate is made electrolyte, contains calcium chloride in the active material of battery; Described calcium chloride is mixed in the cathode material of lithium/thinly chloride battery, and calcium chloride shared mass ratio in the cathode material of lithium/thinly chloride battery is 0.02.
The production method of above-mentioned lithium/thinly chloride battery is: in the production process of the cathode material of lithium/thinly chloride battery, add mass ratio and be 0.02 calcium chloride, make the cathode material of the lithium/thinly chloride battery that contains calcium chloride; In the dry environment of relative humidity≤1%, cathode material, fibreglass diaphragm, the lithium metal anode of the above-mentioned lithium/thinly chloride battery that contains calcium chloride is wound into the battery core body, the battery container of packing in the lump; According to current technology, with the battery girth welding, with lithium/thinly chloride battery electrolyte injection battery and plug-hole soldering and sealing; At last, the lithium/thinly chloride battery that will contain calcium chloride is put into 54 ℃ hot blast bellows and was stored 48 hours, makes finished product.
Embodiment 2
A kind of lithium/thinly chloride battery; With the lithium is anode; Carbon is made cathode carrier, and the thionyl chloride solution of anhydrous tetrachloro-lithium aluminate is made electrolyte, contains calcium chloride in the active material of battery; Described calcium chloride is mixed in the electrolyte material of lithium/thinly chloride battery, and calcium chloride reaches capacity in the electrolyte material of lithium/thinly chloride battery.
The production method of above-mentioned lithium/thinly chloride battery is: in the production process of the electrolyte material of lithium/thinly chloride battery; Add calcium chloride; And calcium chloride reaches capacity in the electrolyte material of lithium/thinly chloride battery, makes the electrolyte material of the lithium/thinly chloride battery that contains calcium chloride; In the dry environment of relative humidity≤1%, cathode material, fibreglass diaphragm, the lithium metal anode of lithium/thinly chloride battery is wound into the battery core body, the battery container of packing in the lump; According to current technology, battery girth welding, the lithium/thinly chloride battery electrolyte that will contain calcium chloride are injected battery and plug-hole soldering and sealing; At last, the lithium/thinly chloride battery that will contain calcium chloride is put into 54 ℃ hot blast bellows and was stored 48 hours, makes finished product.
Embodiment 3
A kind of lithium/thinly chloride battery; With the lithium is anode, and carbon is made cathode carrier, and the thionyl chloride solution of anhydrous tetrachloro-lithium aluminate is made electrolyte; Contain calcium chloride in the active material of battery; Described calcium chloride is mixed in the electrolyte material of the cathode material of lithium/thinly chloride battery and lithium/thinly chloride battery, and calcium chloride shared mass ratio in the cathode material of lithium/thinly chloride battery is 0.01, and calcium chloride reaches capacity in the electrolyte material of lithium/thinly chloride battery.
The production method of above-mentioned lithium/thinly chloride battery is: in the production process of the cathode material of lithium/thinly chloride battery, add mass ratio and be 0.01 calcium chloride, make the cathode material of the lithium/thinly chloride battery that contains calcium chloride; In the production process of the electrolyte material of lithium/thinly chloride battery, add calcium chloride, and calcium chloride reaches capacity in the electrolyte material of lithium/thinly chloride battery, make the electrolyte material of the lithium/thinly chloride battery that contains calcium chloride; In the dry environment of relative humidity≤1%, cathode material, fibreglass diaphragm, the lithium metal anode that will contain the lithium/thinly chloride battery of calcium chloride are wound into the battery core body, the battery container of packing in the lump; According to current technology, battery girth welding, the lithium/thinly chloride battery electrolyte that will contain calcium chloride are injected battery and plug-hole soldering and sealing; At last, the lithium/thinly chloride battery that will contain calcium chloride is put into 54 ℃ hot blast bellows and was stored 48 hours, makes finished product.
In conjunction with the foregoing description, the invention has the beneficial effects as follows: above-mentioned lithium/thinly chloride battery is owing to contain the calcium metal halide in the cell active materials, and the adding of this calcium metal halide is improved the performance of lithium/thinly chloride battery greatly.This is because calcium has preferably open circuit voltage, excellent characteristic such as discharge capacity and anti-preferably thionyl chloride passivation preferably in thionyl chloride.Therefore; Because the adding of calcium metal halide; Effect through cathode active material thionyl chloride in the lithium/thinly chloride battery; Suppress the formation on lithium metal anode surface " passivating film ", made lithium/thinly chloride battery obtain good discharge voltage and discharge capacity, significantly improved the voltage delay phenomenon of lithium/thinly chloride battery.
The above embodiments are the principle and the effect thereof of illustrative the invention only, and the embodiment of part utilization, but not is used to limit the present invention; Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the invention design, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (2)
1. lithium/thinly chloride battery; With the lithium is anode; Carbon is made cathode carrier; The thionyl chloride solution of anhydrous tetrachloro-lithium aluminate is made electrolyte, it is characterized in that: contain the calcium metal halide in the active material of battery, described calcium metal halide is mixed in the cathode material of lithium/thinly chloride battery or/and in the electrolyte material of lithium/thinly chloride battery; And calcium metal halide shared mass ratio in the cathode material of lithium/thinly chloride battery is 0.01 ~ 0.06, and the calcium metal halide reaches capacity in the electrolyte material of lithium/thinly chloride battery.
2. a kind of lithium/thinly chloride battery according to claim 1 is characterized in that: described calcium metal halide is a calcium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101105350A CN102208675B (en) | 2011-04-29 | 2011-04-29 | Lithium/thionyl dichloride battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101105350A CN102208675B (en) | 2011-04-29 | 2011-04-29 | Lithium/thionyl dichloride battery |
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| CN102208675A CN102208675A (en) | 2011-10-05 |
| CN102208675B true CN102208675B (en) | 2012-12-19 |
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| CN2011101105350A Expired - Fee Related CN102208675B (en) | 2011-04-29 | 2011-04-29 | Lithium/thionyl dichloride battery |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103814468B (en) * | 2013-09-27 | 2018-07-06 | 惠州亿纬锂能股份有限公司 | A kind of electrolyte for lithium cells and the lithium battery using the electrolyte |
| CN106229546A (en) * | 2016-10-14 | 2016-12-14 | 苏州金科发能源技术有限公司 | A kind of manufacture method of lithium/thinly chloride battery |
| CN109411817B (en) * | 2018-10-30 | 2020-10-27 | 中南大学 | Lithium ion battery or lithium sulfur battery electrolyte |
| CN115020728B (en) * | 2022-07-12 | 2024-06-07 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Method for eliminating initial voltage hysteresis of lithium thionyl chloride battery in discharge stage |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6187479B1 (en) * | 1998-03-06 | 2001-02-13 | Changle Liu | Ambient temperature, rechargeable cells with metal salt-based electrodes and a system of cell component materials for use therein |
| JP2000077103A (en) * | 1998-08-31 | 2000-03-14 | Hitachi Ltd | Lithium secondary battery and apparatus |
| CN101499526A (en) * | 2009-03-06 | 2009-08-05 | 武汉孚安特科技有限公司 | Lithium-thionyl chloride cell cathode with improved battery voltage hysteretic properties |
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Address after: Suzhou City, Jiangsu province 215618 city of Zhangjiagang Tang town yangshe road Suzhou Jinke Energy Technology Co Ltd Patentee after: Suzhou Jinke Energy Technology Co., Ltd. Address before: Suzhou City, Jiangsu province 215618 city of Zhangjiagang Tang town yangshe road Suzhou Jinke hair lithium battery Patentee before: Suzhou Jinkefa Lithium Battery Co., Ltd. |
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