CN105319321B - 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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- CN105319321B CN105319321B CN201410310302.9A CN201410310302A CN105319321B CN 105319321 B CN105319321 B CN 105319321B CN 201410310302 A CN201410310302 A CN 201410310302A CN 105319321 B CN105319321 B CN 105319321B
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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
The present invention relates in lithium-sulfur cell running the confinement effect to elemental sulfur for the positive electrode detection method, especially
It is related to a kind of detection method of lithium sulfur battery anode material sulfur fixation performance.
Background technology
With developing rapidly of communication, mobile electronic device, electric motor car and space technology, close in the urgent need to exploitation high-energy
The battery of degree.The specific energy of lithium ion battery is less than 200Wh/kg mostly at present, because the specific capacity by existing positive electrode limits
System, 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 has
Necessary exploitation a new generation electrochemical energy storage system is to solve or to alleviate problems.In new energy storage system, with lithium metal it is
Negative pole, elemental sulfur are the lithium-sulfur rechargeable battery of positive pole, and theoretical specific energy is up to 2600Wh/kg, about the 5 of conventional lithium ion battery
Times, can reach 400～600Wh/kg at present, far above traditional commerce secondary cell.Additionally, its positive active material sulfur comes
Source is abundant, cheap, can be greatly lowered battery cost, have larger market prospect.Therefore, from specific energy and commercial value two
Individual angle is seen, lithium-sulfur cell has become current most one of secondary cell system of captivation, causes domestic and international research work
The extensive concern of person.
However, also there are a lot of problems in the development of lithium-sulfur cell.I.e. positive active material utilization efficiency is low, circulation volume declines
The problems such as subtract serious is the subject matter that current lithium-sulfur cell itself exists, and it is mainly led to by the lithium sulfide that course of reaction generates
Often it is attached to sulfur surface, and the electric conductivity of sulfur and lithium sulfide is poor, therefore hinder sulfur to react further, so that the utilization rate of elemental sulfur is dropped
Low；Next, the intermediate product Li generating in sulfur reduction or lithium sulfide oxidizing process2Sn(3≤n≤6) are all dissolved in electrolyte, one
As can through barrier film diffuse to cathode of lithium generate insoluble Li2S or Li2S2, cause active substance to lose, lead to circulating battery
Bad stability；Furthermore, due to sulfur (2.07g/cm3) and Li2S(1.66g/cm3) density variation is larger, just lead to before and after reaction
Pole material deformation is notable, thus destroying electrode structure, the final cyclical stability reducing battery.
For the problems referred to above, domestic and international researcher is mainly carried out in terms of positive electrode, electrolyte and cathode of lithium protection etc.
Research.1) in terms of positive electrode, studied mainly for cathode material structure, such as：Introduce microporous carbon, mesoporous carbon and
Multi-stage porous carbon is as load sulfenyl body, the coated porous carbon of conducting polymer-sulfur nano-complex etc..Its purpose is all to lead in solution sulfur
On the basis of electrically poor, polysulfide is suppressed to flow out positive pole by introducing physically or chemically barrier.2) in terms of electrolyte, mainly
Modified (such as existing electrolyte component：Add the additives such as lithium nitrate, screening solvent) and exploitation Novel electrolytic liquid system
(such as：Ionic liquid, solid electrolyte, double-deck electrolyte etc.).3) in terms of cathode of lithium protection, it is mainly reflected in cathode of lithium table
Face is modified[20].Find from previous karyotype studies, with rear compared with both, the impact to battery performance for the positive electrode is more aobvious
Write, therefore the related research of current lithium-sulfur cell focuses mostly in terms of the solid sulfur of positive electrode.
At present, the method for the sulfur fixation performance of test positive electrode is mainly carried out by battery testing, obtained by the method
Message reflection be the critical components such as positive electrode, electrolyte, barrier film combination property, can not come up intuitively from intrinsic
Feedback positive electrode itself sulfur fixation performance, therefore, set up a set of intuitively, can from intrinsic upper reflection positive electrode sulfur fixation performance
Method imperative.
Content of the invention
It is an object of the invention to provide a kind of method from intrinsic upper sign material sulfur fixation performance；This method of testing is simple
Easily-controllable, accuracy is high, reproducible, can accurate characterization positive electrode under battery actual motion condition be imitated by the confinement of elemental sulfur
Really.
To achieve these goals, the technical scheme of present invention offer is：
A kind of detection method of lithium sulfur battery anode material sulfur fixation performance, the method includes qualitative analyses and quantitative analyses two
Part,
A, qualitative analyses are carried out by electrode pattern tester, will not carry out the positive pole of circulating battery application and circulation should
Filled in respectively in electrode pattern tester with the positive pole under the charging done state of more than 1 time, observe sulfur pattern in electrode, and
It is compared the situation of change being circulated sulfur pattern in before and after's electrode, tentatively judge positive electrode captured sulfur result；
B, quantitative analyses are carried out by thermal analyzer, comprise the steps；
(1) take the elemental sulfur of 2-50mg, fill in thermal analyzer loading crucible, with 2 DEG C/min heating rate from room temperature
It is warming up to 600 DEG C, 600 DEG C of constant temperature 10-60min roastings, obtain the quality-temperature curve of elemental sulfur distillation completely, obtain simple substance
The minimum temperature point of sulfur distillation completely just；
(2) take the binding agent of 2-50mg, fill in thermal analyzer loading crucible, with 2 DEG C/min heating rate from room temperature
It is warming up to the minimum temperature point of elemental sulfur distillation completely just, in the minimum temperature point constant temperature 10- of elemental sulfur distillation completely just
60min roasting, obtains the percentage of binding agent mass loss under elemental sulfur just the minimum temperature point treatment conditions of distillation completely
Amount x%；
(3) from aluminium foil, the positive pole not carrying out circulating battery for m for the scraping quality fills in thermal analyzer loading crucible,
Process by step (1) heating schedule, with 2 DEG C/min heating rate from room temperature to the lowest temperature of elemental sulfur distillation completely just
Degree point, in the minimum temperature point constant temperature 10-60min roasting of elemental sulfur distillation completely just, obtains the matter of positive electrode in positive pole
Amount m0, by calculating (m-m0Binder content × x% in-m × positive pole)/m, obtain elemental sulfur in positive electrode before circulating battery
Weight/mass percentage composition m1%；
(4) by positive pole assemble in the battery, battery tester is carried out n (n is the integer more than or equal to 1) secondary more than
Cyclical stability test, take positive pole under charging done state after circulation, after being dried with electrolyte solvent washing, scraping positive pole is filled out
In thermal analyzer loading crucible, by step (3) heating schedule and data processor, obtain in positive electrode after circulating battery
The weight/mass percentage composition m of elemental sulfur2%, that is, obtain circulating the loss weight/mass percentage composition (m of elemental sulfur in n rear electrode1-
m2) %.
Described sulfur pattern includes sulfur in the distribution (uniformity coefficient being distributed) of electrode surface and the size of sulfur granules；
Relatively circulate sulfur granules in front electrode by sulfur granules in contrast circulation rear electrode and diminish degree, the big degree of change or sulfur granules distribution all
The degree that even property is deteriorated, the captured sulfur result of the existing positive electrode of equal Crestor gonosome, intensity of variation is bigger, and the solid sulfur of positive electrode is described
Effect is poorer；Described sulfur granules distributing homogeneity refer to sulfur granules in unit area dense degree (Fig. 4 be sulfur granules pattern become
Change schematic diagram).
Described positive electrode is one of porous carbon materials, conducting polymer, metal-oxide or two or more mixing
Thing；Described sulfur is elemental sulfur；
Wherein porous carbon materials are activated carbon, charcoal-aero gel, Graphene, graphite oxide, expanded graphite, CNT, carbon
One of nanofiber, mesoporous carbon or two or more mixture；
Conducting polymer is one of polyaniline, polypyrrole, polythiophene or two or more；
Metal-oxide is one of yittrium oxide, lanthana, cerium oxide, titanium oxide or two or more.
Described positive pole is to scratch to collector positive electrode with the complex of elemental sulfur and the mixed slurry of binding agent
Or form from roll-in, it is added with mixed slurry or without conductive agent；Wherein conductive agent is acetylene black, white carbon black, graphite, carbon receives
One of mitron, carbon nano-fiber, mesoporous carbon or more than two kinds, collector is aluminium foil, in carbon paper, carbon cloth, nickel foam one
Kind；
Described binding agent is politef, Kynoar, polyvinyl alcohol, sodium carboxymethyl cellulose, polyacrylic
One or more；Described electrolyte solvent is DOX, tetraethylene glycol dimethyl ether, glycol dimethyl ether, dimethyl sulfoxide
One or more of.
Described tester be laser microscope, scanning electron microscope or scanning projection electron microscope；
Described battery tester is blue electricity 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℃/min；Mass resolution is 0.2mg；Described crucible is made up of one of aluminium sesquioxide, platinum, gold material.
The present invention has advantages below 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, enables
The sulfur capturing capacity of in-situ characterization positive electrode, accurately reflects the confinement effect to elemental sulfur for the material；
(2) this method of testing is more directly perceived, and simple and easy to control, accuracy is high, reproducible, and energy accurate characterization is in actual motion
Under the conditions of positive electrode captured sulfur result.
Brief description
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 morphology change schematic diagram.
Specific embodiment
Illustrate embodiments of the present invention with reference to embodiment, it is specific that certain present invention is not limited in these
Embodiment.
Embodiment 1
The positive pole A that brand-new is got ready is assembled into button cell, connects and carries out circulating battery test to blue electric tester, follows
After ring 5 times and charging terminates, battery is taken apart in glove box, take out positive pole B, after being rinsed for several times with DOX,
After producing 70 DEG C of drying, carry out characterization test.
Qualitative analyses：Positive pole B under positive pole A and 5 cycle charging done states is filled in scanning electron microscope respectively
The change (shown in Fig. 1) of electrode pattern before and after middle test battery operation.As seen from Figure 1, before and after circulation, material surface occurs
Obvious change, before circulation, material surface is more smooth, there are no obvious sulfur granules and exists, after circulation, material surface is obvious
There is the attachment of elemental sulfur, after illustrating to circulate 5 times, this positive electrode is poor to the confinement crystallized ability of elemental sulfur.
Quantitative analyses：Take the elemental sulfur of 2mg, fill in thermal analyzer loading crucible, room temperature～600 DEG C, 2 DEG C/min liter
Warm speed roasting, 600 DEG C of constant temperature 10min, when determining 600 DEG C, elemental sulfur is gasified totally, and residual mass is 0；Take gluing of 2mg
Knot agent, is processed by step 1 method, obtains binding agent PVDF mass loss x% under above-mentioned treatment conditions and (processes final temperature for 420
DEG C when, x=0)；The positive pole A (quality of positive electrode+elemental sulfur is about 5mg) not carrying out circulating battery in right amount is taken to fill in heat
In analyser loading crucible, process to 420 DEG C by step 1 heating schedule, obtain elemental sulfur in positive electrode before circulating battery
Content 75% (weight loss is sulfur content)；By positive pole B with, after the drying of electrolyte solvent washing, filling in thermal analyzer loading crucible
Interior, process 420 DEG C by step 1 heating schedule, obtain the content 38% of elemental sulfur in positive electrode after battery difference cycle-index,
Obtain loss amount (37) % circulating elemental sulfur in 5 rear electrodes.As shown in Figure 2.Illustrate this material after circulating battery 5 times
Elemental sulfur content in the material is 38%, illustrates that the sulfur capturing capacity of this positive electrode is poor.Fig. 4 is sulfur granules in cyclic process
Pattern it may happen that situation of change, if occur above-mentioned situation, all can embody the captured sulfur result of material, phenomenon is more obvious, Gu sulfur
Effect is poorer.
Claims (6)
1. a kind of detection method of lithium sulfur battery anode material sulfur fixation performance it is characterised in that：The method include qualitative analyses and
Quantitative analyses two parts：
A, qualitative analyses are carried out by electrode pattern tester, will not carry out positive pole and the cycle applications 1 of circulating battery application
Positive pole under secondary above charging done state fills in electrode pattern tester respectively, observes sulfur pattern in electrode, goes forward side by side
Row compares the situation of change being circulated sulfur pattern in before and after's electrode, tentatively judges positive electrode captured sulfur result；
B, quantitative analyses are carried out by thermal analyzer, comprise the steps：
(1) take the elemental sulfur of 2-50mg, 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 roastings, obtain the quality-temperature curve of elemental sulfur distillation completely, obtain elemental sulfur proper
The well minimum temperature point of distillation completely；
(2) take the binding agent of 2-50mg, fill in thermal analyzer loading crucible, with 2 DEG C/min heating rate from room temperature
To the minimum temperature point of elemental sulfur distillation completely just, in the minimum temperature point constant temperature 10-60min of elemental sulfur distillation completely just
Roasting, obtains percentage amounts x% of binding agent mass loss under elemental sulfur just the minimum temperature point treatment conditions of distillation completely；
(3) from aluminium foil, the positive pole not carrying out circulating battery for m for the scraping quality fills in thermal analyzer loading crucible, by step
Suddenly (1) heating schedule is processed, with 2 DEG C/min heating rate from room temperature to the minimum temperature of elemental sulfur distillation completely just
Point, in the minimum temperature point constant temperature 10-60min roasting of elemental sulfur distillation completely just, obtains positive electrode and remnants in positive pole
Binding agent gross mass m0, by calculating (m-m0Binder content × x% in-m × positive pole)/m, just obtain before circulating battery
The weight/mass percentage composition m of elemental sulfur in the material of pole1%；(4) positive pole is assembled in the battery, n is carried out on battery tester
Secondary above cyclical stability test, takes the positive pole under charging done state after circulation, after being dried with electrolyte solvent washing, scrapes
Take positive pole to fill in thermal analyzer loading crucible, by step (3) heating schedule and data processor, just obtain after circulating battery
The weight/mass percentage composition m of elemental sulfur in the material of pole2%, that is, the loss percent mass obtaining circulating elemental sulfur in n rear electrode contains
Amount (m1-m2) %, wherein n is the integer more than or equal to 1.
2. detection method according to claim 1 it is characterised in that：Sulfur pattern includes the distribution in electrode surface for the sulfur
And the size of sulfur granules；By contrast circulation rear electrode in sulfur granules relatively circulate sulfur granules in front electrode diminish degree, become great Cheng
Degree or the degree of sulfur granules distributing homogeneity variation, the captured sulfur result of the existing positive electrode of equal Crestor gonosome, intensity of variation is bigger, says
The captured sulfur result of bright 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 it is characterised in that：Described positive electrode is porous carbon materials, conduction is poly-
One of compound, metal-oxide or two or more mixture；Described sulfur is elemental sulfur；Wherein porous carbon materials are activity
One of charcoal, charcoal-aero gel, Graphene, graphite oxide, expanded graphite, CNT, carbon nano-fiber, mesoporous carbon or two kinds
Thing mixed above；Conducting polymer is one of polyaniline, polypyrrole, polythiophene or two or more；Metal-oxide is oxygen
Change one of yttrium, lanthana, cerium oxide, titanium oxide or two or more.
4. detection method according to claim 3 it is characterised in that：Described positive pole is answering positive electrode and elemental sulfur
The mixed slurry of compound and binding agent scratches to collector or forms from roll-in, is added with or without leading in mixed slurry
Electric agent；Wherein conductive agent be one of acetylene black, white carbon black, graphite, CNT, carbon nano-fiber, mesoporous carbon or two kinds with
On, collector is one of aluminium foil, carbon paper, carbon cloth, nickel foam；Described binding agent is politef, Kynoar, poly-
Vinyl alcohol, sodium carboxymethyl cellulose, polyacrylic one or more；Described electrolyte solvent is DOX, four sweet
One or more of diethylene glycol dimethyl ether, glycol dimethyl ether, dimethyl sulfoxide.
5. detection method according to claim 1 it is characterised in that：Described tester is laser microscope, scanning electron
Microscope or scanning projection electron microscope；Described battery tester is blue electricity cell tester or Arbin battery testing
Instrument.
6. detection method according to claim 1 it is characterised in that：Described thermal analyzer is weight analyzer or differential thermal divides
Analyzer, 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 three
One of Al 2 O, platinum, gold material is made.
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| A Microsized Cagelike Sulfur/Carbon Composite for a Lithium/Sulfur Battery with Excellent Performance;Meiri Wang et al;《ChemPlusChem》;20140514;第79卷;全文 * |
| 硫/多孔碳复合正极材料的研究;张文华;《武汉大学博士学位论文》;20140115;全文 * |
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