CN105319321A - Detection method of sulfur fixation performance of lithium sulfur battery cathode material - Google Patents
Detection method of sulfur fixation performance of lithium sulfur battery cathode material Download PDFInfo
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- CN105319321A CN105319321A CN201410310302.9A CN201410310302A CN105319321A CN 105319321 A CN105319321 A CN 105319321A CN 201410310302 A CN201410310302 A CN 201410310302A CN 105319321 A CN105319321 A CN 105319321A
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Abstract
The invention relates to a detection method of the sulfur fixation performance of a lithium sulfur battery cathode material. The detection method employs a sulfur content test device and a sulfur electrode appearance change test device to detect dissolving and losing situation of elementary sulfur in an operation process of the battery. The cathode materials in different charging/discharging status during a circulating test process are placed in the sulfur content test device to obtain the loading quantity of the elementary sulfur in the cathode materials under the status. Meanwhile, the sulfur electrode appearance change test device is employed for testing the change of appearance of the electrode to obtain the sulfur fixation capability of the cathode materials in an essentially representation manner. The detection method can achieve in-situ representation of the sulfur fixation performance of the cathode material, can accurately reflect a confinement effect of the material to the elementary sulfur, is simple and easy-to-control in test processes and is good in repeatability.
Description
Technical field
To the present invention relates in lithium-sulfur cell operational process positive electrode to the detection method of the confinement effect of elemental sulfur, particularly a kind of detection method of lithium sulfur battery anode material sulfur fixation performance.
Background technology
Along with the develop rapidly of communication, mobile electronic device, electric motor car and space technology, in the urgent need to developing the battery of high-energy-density.The specific energy of current lithium ion battery is mostly lower than 200Wh/kg, owing to limiting by the specific storage of existing positive electrode, its specific energy difficulty has a distinct increment, and the approach relying on high charge voltage increase specific energy will aggravate security of system, therefore be necessary that Development of New Generation electrochemical energy storage system is to solve or to alleviate problems.In new energy storage system, take lithium metal as negative pole, the elemental sulfur lithium-sulfur rechargeable battery that is positive pole, theoretical specific energy can reach 2600Wh/kg, is about 5 times of conventional lithium ion battery, 400 ~ 600Wh/kg can be reached, far above traditional commerce secondary cell at present.In addition, its positive active material sulphur abundance, cheap, can greatly reduce battery cost, have larger market outlook.Therefore, from specific energy and commercial value two angles, lithium-sulfur cell has become one of secondary cell system of current most attractive force, causes the extensive concern of domestic and international research worker.
But also there is a lot of problem in the development of lithium-sulfur cell.The problems such as namely positive active material utilization efficiency is low, Capacity fading is serious are the subject matter that current lithium-sulfur cell itself exists, its lithium sulfide mainly generated by course of reaction is attached to sulphur surface usually, and the electric conductivity of sulphur and lithium sulfide is poor, therefore hinder sulphur to react further, the utilization factor of elemental sulfur is reduced; Next, the intermediate product Li that sulphur reduces or generates in lithium sulfide oxidizing process
2s
n(3≤n≤6) are all dissolved in electrolytic solution, and it generally can diffuse to cathode of lithium through barrier film and generate insoluble Li
2s or Li
2s
2, cause active substance to lose, cause circulating battery bad stability; Moreover, due to sulphur (2.07g/cm
3) and Li
2s (1.66g/cm
3) density variation is comparatively large, cause positive electrode deformation before and after reaction remarkable, thus destroy electrode structure, the final cyclical stability reducing battery.
For the problems referred to above, domestic and international researcher is mainly studied from aspects such as positive electrode, electrolytic solution and cathode of lithium protections.1) in positive electrode, study mainly for cathode material structure, such as: introduce microporous carbon, mesoporous carbon and multi-stage porous carbon as carrying sulfenyl body, conducting polymer coated porous carbon-sulphur nano-complex etc.Its object is all on the basis solving sulphur poorly conductive, by introducing physics or chemical barrier suppression polysulfide outflow positive pole.2) in electrolytic solution, mainly for existing electrolyte component modification (as: adding the adjuvants such as lithium nitrate, screening solvent) and development of new electrolyte system (as: ionic liquid, solid electrolyte, double-deck electrolytic solution etc.).3) in cathode of lithium protection, be mainly reflected in and cathode of lithium surface is modified
[20].Find from previous karyotype studies, compared with both rear, positive electrode is more remarkable on the impact of battery performance, therefore the research that lithium-sulfur cell is relevant at present focuses mostly in the solid sulphur of positive electrode.
At present, the method of the sulfur fixation performance of test positive electrode is mainly undertaken by battery testing, the message reflection that the method obtains be the combination property of the critical components such as positive electrode, electrolytic solution, barrier film, the sulfur fixation performance of positive electrode itself can not be fed back intuitively from intrinsic, therefore, set up intuitively a set of, can reflect that the method for positive electrode sulfur fixation performance is imperative from intrinsic.
Summary of the invention
The object of the present invention is to provide a kind of method from exosyndrome material sulfur fixation performance intrinsic; This method of testing is simple and easy to control, accuracy is high, reproducible, can accurate characterization under battery actual motion condition positive electrode to the confinement effect of elemental sulfur.
To achieve these goals, technical scheme provided by the invention is:
A detection method for lithium sulfur battery anode material sulfur fixation performance, the method comprises qualitative analysis and quantitative test two parts,
A, qualitative analysis are undertaken by electrode pattern tester, the positive pole being about to not carry out under the positive pole of circulating battery application and the charging done state of cycle applications more than 1 time fills in electrode pattern tester respectively, observe sulphur pattern in electrode, and compare the situation of change obtaining sulphur pattern in electrode before and after circulation, tentatively judge positive electrode captured sulfur result;
B, quantitative test are undertaken by thermal analyzer, comprise the steps;
(1) elemental sulfur of 2-50mg is got, fill in thermal analyzer loading crucible, with 2 DEG C/min heating rate from room temperature to 600 DEG C, 600 DEG C of constant temperature 10-60min roasting, obtain quality-temperature curve that elemental sulfur distils completely, obtain the minimum temperature point that elemental sulfur distils just completely;
(2) cementing agent of 2-50mg is got, fill in thermal analyzer loading crucible, with the minimum temperature point that 2 DEG C/min heating rate distils just completely from room temperature to elemental sulfur, in the minimum temperature point constant temperature 10-60min roasting that elemental sulfur distils just completely, obtain the percentage amounts x% of mass loss under the minimum temperature point treatment conditions that cementing agent distils just completely at elemental sulfur;
(3) positive pole not carrying out circulating battery being m from scraping quality aluminium foil fills in thermal analyzer loading crucible, by step (1) heating schedule process, with the minimum temperature point that 2 DEG C/min heating rate distils just completely from room temperature to elemental sulfur, in the minimum temperature point constant temperature 10-60min roasting that elemental sulfur distils just completely, obtain the quality m of positive electrode in positive pole
0, by calculating (m-m
0binder content × x% in-m × positive pole)/m, obtain the mass percentage m of elemental sulfur in positive electrode before circulating battery
1%;
(4) by positive pole assembling in the battery, battery tester carries out n (n be more than or equal to 1 integer) secondary more than cyclical stability test, getting circulation after charging done state under positive pole, after drying with electrolytic solution solvent washing, scraping positive pole fills in thermal analyzer loading crucible, by step (3) heating schedule and data processor, obtain the mass percentage m of elemental sulfur in positive electrode after circulating battery
2%, namely obtains the loss mass percentage (m of elemental sulfur in circulation n rear electrode
1-m
2) %.
Described sulphur pattern comprises the distribution (degree of uniformity that namely distribute) of sulphur at electrode surface and the size of sulfur granules; By sulfur granules in contrast circulation rear electrode comparatively circulate sulfur granules in front electrode diminish degree, become the degree that large degree or sulfur granules distributing homogeneity be deteriorated, all can the captured sulfur result of qualitative embodiment positive electrode, intensity of variation is larger, illustrates that the captured sulfur result of positive electrode is poorer; Described sulfur granules distributing homogeneity refers to the dense degree (Fig. 4 is sulfur granules pattern change schematic diagram) of sulfur granules in unit area.
Described positive electrode is one or more potpourris in porous carbon materials, conducting polymer, metal oxide; Described sulphur is elemental sulfur;
Wherein porous carbon materials is one or more potpourris in activated charcoal, charcoal-aero gel, Graphene, graphite oxide, expanded graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon;
Conducting polymer is one or more in polyaniline, polypyrrole, polythiophene;
Metal oxide is one or more in yttria, lanthana, cerium oxide, titanium dioxide.
Described positive pole is formed to collector or from roll-in positive electrode and the compound of elemental sulfur and the mixed slurry blade coating of cementing agent, is added with or do not add conductive agent in mixed slurry; Wherein conductive agent is one or two or more kinds in acetylene black, carbon black, graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon, and collector is the one in aluminium foil, carbon paper, carbon cloth, nickel foam;
Described cementing agent be teflon, Kynoar, polyvinyl alcohol (PVA), sodium carboxymethyl cellulose, polyacrylic one or more; Described electrolyte solvent is one or more in DOX, tetraethylene glycol dimethyl ether, glycol dimethyl ether, dimethyl sulfoxide (DMSO).
Described tester is laser microscope, scanning electron microscope or scanning projection electron microscope;
Described battery tester is blue electric cell tester or Arbin cell tester.
Described thermal analyzer is weight analyzer or differential thermal analyzer, and its temperature range is 0-1000 DEG C, and heating rate is 1-50 DEG C/min; Mass resolution is 0.2mg; Described crucible is that a kind of material in alundum (Al2O3), platinum, gold is made.
The present invention has the following advantages compared with the existing methods:
(1) what the method characterized is the intrinsic performance of material, eliminates the interference of miscellaneous part factor in battery, can realize the sulfur capturing capacity of in-situ characterization positive electrode, and accurately reflection material is to the confinement effect of elemental sulfur;
(2) this method of testing is relatively directly perceived, simple and easy to control, accuracy is high, reproducible, can the captured sulfur result of accurate characterization positive electrode under actual motion condition.
Accompanying drawing explanation
Fig. 1 is the detection figure of qualitative characterization's positive electrode sulfur fixation performance;
Fig. 2 is the detection figure of quantitatively characterizing positive electrode sulfur fixation performance;
Fig. 3 is the overhaul flow chart of positive electrode captured sulfur result;
Fig. 4 is sulfur granules pattern change schematic diagram.
Embodiment
Illustrate embodiments of the present invention below in conjunction with embodiment, certain the present invention is not limited in these specific embodiments.
Embodiment 1
The positive pole A newly prepared is assembled into button cell, is connected in blue electric tester and carries out circulating battery test, to circulate 5 times and after charging and terminating, battery is taken apart in glove box, takes out positive pole B, with 1,3-dioxolanes rinses for several times, after producing 70 DEG C of oven dry, carries out characterization test.
Qualitative analysis: positive pole B under positive pole A and 5 cycle charging done state is filled in respectively the change (shown in Fig. 1) that test battery in scanning electron microscope runs front and back electrode pattern.As seen from Figure 1, before and after circulation, material surface there occurs obvious change, before circulation, material surface is more smooth, exists, after circulation there are no obvious sulfur granules, material surface obviously has the attachment of elemental sulfur, and after circulation 5 times is described, the confinement crystallized ability of this positive electrode to elemental sulfur is poor.
Quantitative test: the elemental sulfur getting 2mg, fills in thermal analyzer loading crucible, room temperature ~ 600 DEG C, the roasting of 2 DEG C/min heating rate, 600 DEG C of constant temperature 10min, and when determining 600 DEG C, elemental sulfur is gasified totally, and residual mass is 0; Get the cementing agent of 2mg, by the process of step 1 method, obtain cementing agent PVDF mass loss x% (when process final temperature is 420 DEG C, x=0) under above-mentioned treatment conditions; Getting the positive pole A (quality of positive electrode+elemental sulfur is about 5mg) not carrying out circulating battery in right amount fills in thermal analyzer loading crucible, by the process to 420 DEG C of step 1 heating schedule, obtain the content 75% (weight loss and sulfur content) of elemental sulfur in positive electrode before circulating battery; After positive pole B is dried with electrolytic solution solvent washing, fill in thermal analyzer loading crucible, by step 1 heating schedule process 420 DEG C, obtain the content 38% of elemental sulfur in positive electrode after the different cycle index of battery, namely obtain loss amount (37) % of elemental sulfur in circulation 5 rear electrodes.As shown in Figure 2.Illustrate that this material elemental sulfur content in the material after circulating battery 5 times is 38%, illustrate that the sulfur capturing capacity of this positive electrode is poor.Fig. 4 is the contingent situation of change of sulfur granules pattern in cyclic process, if there is above-mentioned situation, all can embody the captured sulfur result of material, phenomenon is more obvious, and captured sulfur result is poorer.
Claims (6)
1. a detection method for lithium sulfur battery anode material sulfur fixation performance, is characterized in that: the method comprises qualitative analysis and quantitative test two parts:
A, qualitative analysis are undertaken by electrode pattern tester, the positive pole being about to not carry out under the positive pole of circulating battery application and the charging done state of cycle applications more than 1 time fills in electrode pattern tester respectively, observe sulphur pattern in electrode, and compare the situation of change obtaining sulphur pattern in electrode before and after circulation, tentatively judge positive electrode captured sulfur result;
B, quantitative test are undertaken by thermal analyzer, comprise the steps:
(1) elemental sulfur of 2-50mg is got, fill in thermal analyzer loading crucible, with 2 DEG C/min heating rate from room temperature to 600 DEG C, 600 DEG C of constant temperature 10-60min roasting, obtain quality-temperature curve that elemental sulfur distils completely, obtain the minimum temperature point that elemental sulfur distils just completely;
(2) cementing agent of 2-50mg is got, fill in thermal analyzer loading crucible, with the minimum temperature point that 2 DEG C/min heating rate distils just completely from room temperature to elemental sulfur, in the minimum temperature point constant temperature 10-60min roasting that elemental sulfur distils just completely, obtain the percentage amounts x% of mass loss under the minimum temperature point treatment conditions that cementing agent distils just completely at elemental sulfur;
(3) positive pole not carrying out circulating battery being m from scraping quality aluminium foil fills in thermal analyzer loading crucible, by step (1) heating schedule process, with the minimum temperature point that 2 DEG C/min heating rate distils just completely from room temperature to elemental sulfur, in the minimum temperature point constant temperature 10-60min roasting that elemental sulfur distils just completely, obtain the quality m of positive electrode in positive pole
0, by calculating (m-m
0binder content × x% in-m × positive pole)/m, obtain the mass percentage m of elemental sulfur in positive electrode before circulating battery
1%;
(4) by positive pole assembling in the battery, battery tester carries out n (n be more than or equal to 1 integer) secondary more than cyclical stability test, get the positive pole under circulation rear charging done state, after drying with electrolytic solution solvent washing, scraping positive pole fills in thermal analyzer loading crucible, by step (3) heating schedule and data processor, obtain the mass percentage m of elemental sulfur in positive electrode after circulating battery
2%, namely obtains the loss mass percentage (m of elemental sulfur in circulation n rear electrode
1-m
2) %.
2. detection method according to claim 1, is characterized in that:
Sulphur pattern comprises the distribution (degree of uniformity that namely distribute) of sulphur at electrode surface and the size of sulfur granules;
By sulfur granules in contrast circulation rear electrode comparatively circulate sulfur granules in front electrode diminish degree, become the degree that large degree or sulfur granules distributing homogeneity be deteriorated, all can the captured sulfur result of qualitative embodiment positive electrode, intensity of variation is larger, illustrates that the captured sulfur result of positive electrode is poorer;
Described sulfur granules distributing homogeneity refers to the dense degree of sulfur granules in unit area.
3. detection method according to claim 1, is characterized in that:
Described positive electrode is one or more potpourris in porous carbon materials, conducting polymer, metal oxide; Described sulphur is elemental sulfur;
Wherein porous carbon materials is one or more potpourris in activated charcoal, charcoal-aero gel, Graphene, graphite oxide, expanded graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon;
Conducting polymer is one or more in polyaniline, polypyrrole, polythiophene;
Metal oxide is one or more in yttria, lanthana, cerium oxide, titanium dioxide.
4. detection method according to claim 3, is characterized in that: described positive pole is formed to collector or from roll-in positive electrode and the compound of elemental sulfur and the mixed slurry blade coating of cementing agent, is added with or do not add conductive agent in mixed slurry; Wherein conductive agent is one or two or more kinds in acetylene black, carbon black, graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon, and collector is the one in aluminium foil, carbon paper, carbon cloth, nickel foam;
Described cementing agent be teflon, Kynoar, polyvinyl alcohol (PVA), sodium carboxymethyl cellulose, polyacrylic one or more; Described electrolyte solvent is one or more in DOX, tetraethylene glycol dimethyl ether, glycol dimethyl ether, dimethyl sulfoxide (DMSO).
5. detection method according to claim 1, is characterized in that: described tester is laser microscope, scanning electron microscope or scanning projection electron microscope;
Described battery tester is blue electric cell tester or Arbin cell tester.
6. detection method according to claim 1, is characterized in that: described thermal analyzer is weight analyzer or differential thermal analyzer, and its temperature range is 0-1000 DEG C, and heating rate is 1-50 DEG C/min; Mass resolution is 0.2mg; Described crucible is that a kind of material in alundum (Al2O3), platinum, gold is made.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113608135A (en) * | 2021-06-21 | 2021-11-05 | 天津力神电池股份有限公司 | Method for prejudging circulating water jumping of lithium ion generation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130171734A1 (en) * | 2011-12-28 | 2013-07-04 | Soulbrain Co., Ltd. | Method of Measuring Moisture Content in Lithium Secondary Battery Electrolyte and Analytical Reagent Composition Used in the Same |
| CN103413945A (en) * | 2013-08-27 | 2013-11-27 | 昆明理工大学 | Manufacturing method of positive material for lithium ion battery |
| CN103472401A (en) * | 2013-09-09 | 2013-12-25 | 东莞新能源科技有限公司 | Detection method for specific capacity of lithium ion battery negative electrode active material after circulation |
-
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- 2014-07-01 CN CN201410310302.9A patent/CN105319321B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130171734A1 (en) * | 2011-12-28 | 2013-07-04 | Soulbrain Co., Ltd. | Method of Measuring Moisture Content in Lithium Secondary Battery Electrolyte and Analytical Reagent Composition Used in the Same |
| CN103413945A (en) * | 2013-08-27 | 2013-11-27 | 昆明理工大学 | Manufacturing method of positive material for lithium ion battery |
| CN103472401A (en) * | 2013-09-09 | 2013-12-25 | 东莞新能源科技有限公司 | Detection method for specific capacity of lithium ion battery negative electrode active material after circulation |
Non-Patent Citations (2)
| Title |
|---|
| MEIRI WANG ET AL: "A Microsized Cagelike Sulfur/Carbon Composite for a Lithium/Sulfur Battery with Excellent Performance", 《CHEMPLUSCHEM》 * |
| 张文华: "硫/多孔碳复合正极材料的研究", 《武汉大学博士学位论文》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113608135A (en) * | 2021-06-21 | 2021-11-05 | 天津力神电池股份有限公司 | Method for prejudging circulating water jumping of lithium ion generation |
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