CN102810679B - Lithium-ferrous disulfide battery - Google Patents
Lithium-ferrous disulfide battery Download PDFInfo
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- CN102810679B CN102810679B CN201210295162.3A CN201210295162A CN102810679B CN 102810679 B CN102810679 B CN 102810679B CN 201210295162 A CN201210295162 A CN 201210295162A CN 102810679 B CN102810679 B CN 102810679B
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Abstract
The invention discloses a lithium-ferrous disulfide battery which comprises a cathode made of lithium metal or lithium metal alloy, an anode made of anode active material of ferrous disulfide, and organic electrolyte. A diaphragm is disposed between the cathode and the anode. The lithium-ferrous disulfide battery is characterized in that electrical conductivity of the organic electrolyte is not larger than 6.5 mS/cm; and the organic electrolyte comprises organic solvent and lithium salt dissolved in the organic solvent, and the organic solvent is composed of gamma-butyrolactone, 1, 2-dimethoxyethane and 1, 3-dioxolane, wherein a raw material volume ratio of the gamma-butyrolactone to total amount of the 1,2-dimethoxyethane and the 1,3-dioxolane is (0-5): (95-100). The lithium-ferrous disulfide battery guarantees high discharge capacity, and high use safety.
Description
Technical field
The present invention relates to disposable lithium-battery field, particularly, relate to and use ferrous disulfide (FeS
2) as the lithium-iron disulfide (Li/FeS of positive electrode active materials
2) battery, i.e. lithium Fe battery.
Background technology
Lithium battery, owing to having the advantages such as energy density is high, voltage is high, operating temperature range is wide, the life-span is long, has been subject to concern and the attention of more and more people.In more than ten years in the past, lithium battery occupies leading position in once (not chargeable) and secondary (chargeable) Battery Market, is widely used in the portable electric appts such as mobile phone, notebook computer and digital camera.
Battery of lithium-iron disulphide belongs to once (not chargeable) battery, be take ferrous disulfide as positive pole (positive pole) active material, be negative pole (negative pole) active material with lithium metal and take organic electrolyte as the battery of electrolyte.The voltage of this primary cell can reach 1.5V, therefore can substitute now conventional alkaline battery and portable energy source as ordinary consumption electronic equipment uses.In addition, this primary cell also has the specific discharge capacity more much higher than alkaline battery, and cryogenic property is good, lightweight, and therefore it is as the high-power battery of a new generation, and positive more and more welcomed by the people, market prospects are boundless.
But things all has dual character, its advantage often becomes shortcoming in any case.This just needs people to go the relation balanced wherein, plays its maximum advantage as far as possible and overcomes its shortcoming.As above the battery of lithium-iron disulphide addressed, has very high energy, and people only have by having the release of control to its energy to reach the application target of expection.On the contrary, if fault offset is out of control, people will be brought not wish the result occurred, bring safety problem.The safety problem of lithium battery is attached great importance to by lithium battery producers.Lithium battery security incident both domestic and external (as burning, blast etc.) is of common occurrence.Again and again event make lithium battery safety problem alarm bell Chang Ming.Each producer launches further investigation for this problem and inquires into one after another, by carrying out battery structure optimization, increasing the method such as safety guard, strict Controlling Technology, reduces the risk that safety problem occurs, has obtained effective progress.As temperature-sensitive element (PTC) the explosion issues widely using to prevent battery from being caused to prevent cell internal pressure excessive by the use of outside short circuit, cell safety valve and effectively control inside battery moisture to prevent the technical measures such as the combination of water and lithium metal, be all the excellent lithium battery of the relieved use of people and confidence is provided.
Battery of lithium-iron disulphide as the lithium battery of emerging kind, just by positive regard.Even if existing related specy battery is as the research and development such as lithium-manganese dioxide battery and lithium ion battery experience, still not enough to the research of battery of lithium-iron disulphide fail safe aspect.Current research turns one's attention to the discharge performance how improving battery, storage life of improving battery and about in manufacturing process etc. the problem of battery greatly at most.As patent 200580044452.9,200480034479.5,200580044588.X both provides the battery of lithium-iron disulphide how obtaining high power capacity, patent 200880008965.8,201110031246.1 has paid close attention to the problem of pretreatment of battery to increase battery storage performance, and patent 200810016797.9,200910020280.1,200910037961.9 etc. all relate to the manufacturing process of battery of lithium-iron disulphide.Seldom there is the problem relating to and solve battery of lithium-iron disulphide fail safe with new thinking.
The fail safe of battery of lithium-iron disulphide is among the manufacture of battery, storage, transport, the links such as use and waste disposal.For work such as manufacture, transport and storages, be all generally have the producer of specialty to carry out, effectively prevented the generation of safety problem by the control to technology, but battery be finally transfer to non-professional terminal use to use.(electric discharge) and the misuse of general routine are normally used, involved by prior art has had for battery.Control for lithium battery safety problem and the various standards that perform as UN/DOT 38.3, ANSI C18.3, IEC60086-4 and UL1642, need to the transport of lithium battery, user's abuse as overdischarge, charging, external short circuit, fall, the problem such as vibrations control effectively.For the battery of lithium-iron disulphide of high energy, battery is opened due to curiosity or other reasons to prevent user by the packaging structure (shell as hard steel) of general employing close and firm, but desired user carries out using in strict accordance with the use instruction of battery manufacturer and does not abuse just one-sided wish.The short circuit of high energy battery of lithium-iron disulphide can form the sharply release to the energy content of battery.But, outside conventional n-negative pole short circuit can be controlled by the temperature-sensitive element (PTC) arranging positive temperature coefficient in battery structure (circuit), this is due to when battery generation external short circuit, great electric current passes through cell circuit, producing a large amount of heats makes battery temperature raise, and the resistance of the temperature-sensitive element of positive temperature coefficient (PTC) can increase rapidly at a certain temperature thus make whole circuit disconnect, cell reaction is stopped, ensure that the safety of battery under outside short-circuit conditions.But, if the inside positive and negative electrode that battery generation internal short-circuit goes wrong as inside battery barrier film and causes directly is connected, or to be extruded or by the situations such as metal spicule runs through, the temperature-sensitive element of positive temperature coefficient is helpless at battery.Existing battery of lithium-iron disulphide technology is not also shown great attention to this, and one of reason is this situation and safety problem unlike other is come so obvious.In addition, in some cases, as inside battery barrier film existing defects or suffer overall slight extruding, even if there occurs the short circuit problem of inside battery, it is irremediable until there is the event as burning or blast that battery also can not show so.In this case usually accepted with the concept of " self-discharge of battery " by people.Problem is, battery throw in the situation behind market than we imagine more complex, we have to expect battery in the problem suffering to occur under extremely severe treating.The danger of combustion that may cause can cause great threat to the person of an innocent person and property safety, moreover the burning of lithium battery not just can simply can be put out by water, and such problem will seriously destroy the trust of consumer to it.
Therefore, need a kind of lithium Fe battery at present badly, this lithium Fe battery should still guarantee certain fail safe under above-mentioned extreme case, to meet the needs in market, and meets supervision standard.
Summary of the invention
In summary of the invention part, introduce the concept of a series of reduced form, this will further describe in embodiment part.Summary of the invention part of the present invention does not also mean that the key feature and essential features that will attempt to limit technical scheme required for protection, does not more mean that the protection range attempting to determine technical scheme required for protection.
Based on above technical problem, the invention provides a kind of safe battery of lithium-iron disulphide, even if this battery is when suffering severe internal short-circuit as run through (hereinafter referred to as puncture) by metal spicule, being still difficult to burn.
Battery of lithium-iron disulphide of the present invention comprises: the negative pole be made up of lithium metal or its alloy, using ferrous disulfide as the positive pole of positive electrode active materials and containing the organic electrolyte of lithium salts, be provided with barrier film between described negative pole and positive pole; It is characterized in that, described organic electrolyte has the conductivity being not more than 6.5mS/cm; And described organic electrolyte comprises organic solvent and is dissolved in lithium salts wherein, described organic solvent is by gamma-butyrolacton, 1,2-dimethoxy-ethane and 1,3-dioxolane forms, wherein, gamma-butyrolacton is (0-5]: [95-100) relative to the volume feed of 1,2-dimethoxy-ethane and 1,3-dioxolane total amount.
Battery of lithium-iron disulphide of the present invention has excellent fail safe, even if be also difficult in extreme circumstances burning or blast occur, thus have market prospects widely, lithium Fe battery can be made to meet commercial actual demand.
Accompanying drawing explanation
Fig. 1 shows the longitudinal section of battery of lithium-iron disulphide of the present invention.
Embodiment
In the following description, a large amount of concrete details is given to provide more thorough understanding of the invention.But, it will be apparent to one skilled in the art that the present invention can be implemented without the need to these details one or more.In other example, in order to avoid obscuring with the present invention, technical characteristics more well known in the art are not described.
See Fig. 1, battery of lithium-iron disulphide 1 of the present invention comprises positive plate 2, negative plate 4 and barrier film 3.Its manufacture method can be: be coated on plus plate current-collecting body by the slurry containing ferrous disulfide (positive electrode active materials), cut, obtained positive plate 2, then positive plate 2, barrier film 3, the negative plate 4 be made up of lithium metal or its alloy, barrier film 3 is stacked together and winding and form battery core (such as cylindrical battery core), battery core is put into battery container 5, inject organic electrolyte 7 and seal, be i.e. obtained resultant battery (or claiming " new battery " or " brand-new battery ").Wherein also can comprise the positive and negative electrode terminal respectively electric current being guided to battery with positive pole current feed 8 and cathodal current lead-in wire 6.Alternatively, in the hermetically-sealed construction of battery, also can comprise the temperature-sensitive element 9 of positive temperature coefficient and be provided with the explosion-proof sheet metal 10 of pressure switch.
Positive plate 2 includes plus plate current-collecting body and is coated in the anode sizing agent at least one side of plus plate current-collecting body.Wherein, the anode sizing agent of battery of lithium-iron disulphide generally comprises positive pole solid material, binding agent and solvent, and positive pole solid material generally comprises the ferrous disulfide (FeS as positive electrode active materials
2) and conductive agent.Positive electrode active materials also can containing, for example FeS, CoS
2, NiS
2deng transition metal polysulfide.Ferrous disulfide FeS
2content in the solid material of anode sizing agent can be 80% ~ 97% by weight.About ferrous disulfide FeS
2selecting as crystal structure types, conduction type and particle size distribution etc. of material, those skilled in the art can be selected according to the desired technique effect reached.
Above-mentioned conductive agent, for strengthening the electron conduction of positive plate 2, typically can use graphite (natural or artificial), acetylene black, carbon black or its mixture.Its content in the solid material of anode sizing agent can be 1 % by weight-15 % by weight, and this ratio can guarantee that positive plate has enough electron conductions be unlikely to again to take the space of too many positive electrode active materials and affect battery performance.The producer of conductive agent can at home and abroad all can find, as can from TIMICAL or Fujian Shaowu graphite factory etc.
Positive plate 2 uses binding agent, and object is positive electrode active materials is adhered on described plus plate current-collecting body, and ensures that the positive electrode active materials on the positive plate after drying is unlikely to come off and affect battery performance.Binding agent generally uses high molecular polymer, high molecular polymer is dissolved in the bonding glue being formed in solvent and have certain viscosity, can for the anode sizing agent be coated on plus plate current-collecting body to be formed together with positive electrode active materials and conductive agent.There are two kinds of comparatively ripe systems available at present.One is use as from the SEBS(polystyrene-ethylene/butylene-styrene block copolymer of Kraton) binding agent and the Shell A100(aromatic hydrocarbon solvent such as from Shell company) and ShellOMS(isoparaffin) together with form the glue that bonds; It two is use PVDF(Kynoar) with NMP(N-methyl pyrrolidone) and form the glue that bonds.Wherein, the ratio of binding agent in described glue can be 5 % by weight or higher.Based on mentioned component and proportion, the viscosity of anode sizing agent can be adjusted to ideal range so that the carrying out of coating processes by those skilled in the art according to actual needs.Additionally, a kind of and multiple binding agent can also be adopted as required and simultaneously, as long as above-mentioned object can be reached.
The plus plate current-collecting body used in positive plate 2, generally can be formed by one or more metals, its shape is paillon foil or netted, and material can be aluminium, nickel, stainless steel etc., the stainless (steel) wire that the aluminium foil commonly used as used lithium ion battery or lithium-manganese dioxide battery use.Thickness is generally 20 microns even can be thinner as 15 microns, thinks that battery active material provides more space and improves battery performance.
The manufacture process of positive plate 2 is generally as follows: first by active material FeS
2powder mixes with conductive agent graphite, acetylene black, forms positive powder, is mixed by binding agent and form glue with organic solvent.Then positive powder and glue are mixed together the anode sizing agent being formed and can supply to apply.Adopt transfer type or roller coat formula that slurry is evenly coated on plus plate current-collecting body, carry out dry removing organic solvent wherein, form dry positive pole, then carry out roll-in to certain thickness, finally cut into required size.Thus form positive plate 2.
Generally speaking, the manufacture of positive plate 2 can adopt the known method in lithium Fe battery field to carry out, and the ratio more than provided and composition can not be considered as limiting the scope of the invention.
Negative plate 4 in battery 1, its active material is lithium metal Li, pure metal lithium can be used, also alloy that lithium metal and other metals are formed as aluminium can be used to obtain applicable intensity, its shape is preferably foil-like, thickness can be determined according to the principle that the capacity of active material on positive pole relative area carries out mating, and is generally about between 0.15mm to 0.25mm.Length and width can be determined according to battery design and with the relation of positive pole size.
The effect of barrier film 3 is the passage providing inside battery Ion transfer, and the direct electrical contact between isolation positive pole and negative pole is to prevent battery generation internal short-circuit.Its material can adopt the composite membrane of polypropylene (PP), polyethylene (PE) or PP/PE/PP and the micro-porous film of other compositions, conventional can be the sandwich diaphragm obtained from Celgard company, and model is Celgard2400, Celgard2500 etc.
Except above-mentioned execution mode, battery of the present invention also can adopt the basic structure of known conventional battery of lithium-iron disulphide, the battery structure that such as CN101361215A proposes.Except the cylindrical battery shown in Fig. 1, can also adopt the battery configuration such as button, monetary apparatus, battery configuration does not form limiting the scope of the invention.
The electrolyte 7 used in battery 1 is most important for the present invention, and for reaching technique effect of the present invention, manufacture the battery of lithium-iron disulphide that a kind of fail safe is good, the present invention has special requirement to electrolyte 7.Good safety alleged by the present invention, refers to according to lithium battery safety standard SJ/T11170-1998, UL2054:1997, GB/T18287-2000 and the security test that performs.Concrete detection method and requirement will be described in an embodiment.In brief, as described in " background technology " part, refer to that battery is being subject to still possessing certain fail safe in severe inside puncture (internal short-circuit) situation.The present invention by the selection to electrolyte composition, thus achieves the safety of battery in puncture situation, enhances the tolerance of battery to adverse circumstances.
Compared with other batteries, there is certain particularity in lithium-iron disulfide.When battery operated, there is following chemical reaction:
FeS
2+4Li—>Fe+2Li
2S （1）
In fact, when small current discharges, this chemical reaction is divided into two steps to complete:
FeS
2+2Li—>FeS+Li
2S （2）
FeS+2Li—>Fe+Li
2S （3）
This just means that battery is under different operational phases, inside battery has different chemical systems to exist, and when the iron in ferrous disulfide is reduced into after into fe Fe, because the fe granularity being reduced out is less, active extremely strong, considerably increase the conductivity of positive plate.The present inventor's research shows, when having fe to exist, battery is in the most unsafe stage, and after battery is finished using, because the energy content of battery has exhausted substantially, battery transfers safety to.For this reason, inventor's establishing criteria SJ/T11170-1998, UL2054:1997, GB/T18287-2000, and when calculating lithium-iron disulfide reaction, produce the time of fe, be approximately 50% of battery consumption design capacity, i.e. depth of discharge (the Depth of Discharge of 50%, be called for short DOD), represent that battery uses the state to design capacity one half with 50%DOD below.In the present invention, under 50%DOD state, carry out the puncture experiment of battery side, to illustrate that the present invention is for the validity solving battery of lithium-iron disulphide safety problem.
User is after acquisition battery of lithium-iron disulphide, usually can not once battery be finished, but intermittently use, namely battery is likely in any state of 0%DOD to 100%DOD, sum up by experiment and theory analysis draws, precarious position when battery reaches 50%DOD is representative.
For reaching effect of the present invention, the electrolyte 7 that battery 1 uses contains organic solvent and is dissolved in lithium salts wherein.Described organic solvent adopts gamma-butyrolacton (γ-butyrolactone, is abbreviated as GBL), 1,2-dimethoxy-ethane (1,2-Dimethoxyethane, is abbreviated as DME) and 1,3-dioxolane (1,3-Dioxolane, is abbreviated as DIOX) mixed solvent.
This organic solvent is by gamma-butyrolacton, 1,2-dimethoxy-ethane and 1,3-dioxolane forms, wherein, gamma-butyrolacton is relative to 1, the volume feed of 2-dimethoxy-ethane and 1,3-dioxolane total amount is (0-5]: [95-100) (namely the former volume is for being greater than 0 and being less than or equal to 5 parts, and the volume of the latter is for being more than or equal to 95 parts and being less than 100 parts).
Preferably, above-mentioned raw materials volume ratio can be [0.5-5]: [95-99.5];
More preferably, above-mentioned raw materials volume ratio can be [1.5-3]: [97-98.5], to improve the fail safe of battery as much as possible.
Wherein, the volume feed of 1,2-dimethoxy-ethane and 1,3-dioxolane can be 0.25-2:1;
Preferably, the volume feed of 1,2-dimethoxy-ethane and 1,3-dioxolane can be 0.5-1:1, to guarantee the mobility of electrolyte, makes again lithium salts can have good dissociation simultaneously.
Typically, the volume feed of described 1,2-dimethoxy-ethane and 1,3-dioxolane can be about 1:1.In addition, also can be adjusted in above-mentioned scope according to factors such as the costs of material.Various proportion all can realize basic effect of the present invention above.The present invention does not attempt strictly to limit its ratio.
" volume feed " of indication of the present invention refers to two or more raw materials volume ratio at normal temperatures before mixing for mixing, wherein indication be mixing for " volume " compared before initial volume.Wherein, " gamma-butyrolacton is relative to 1; 2-dimethoxy-ethane and 1; volume feed of 3-dioxolane total amount " refers to that gamma-butyrolacton volume is before mixing relative to 1, the volume ratio at normal temperatures of 2-dimethoxy-ethane and 1,3-dioxolane initial volume sum separately, " 1; the volume feed of 2-dimethoxy-ethane and 1,3-dioxolane " refers to these two kinds of solvents volume ratio at normal temperatures before mixing.
Contain lithium salts in electrolyte 7, described lithium salts can from lithium salts as LiTFS (trifluoromethyl sulfonic acid lithium), LiTFSI (two (fluoroform sulphonyl) imine lithium), LiI, LiBr, LiBF
4, LiClO
4and LiPF
6in select one or more.Wherein, lithium iodide (LiI) preferably comprises, and more preferably this lithium salts comprises the lithium iodide of more than 90 % by mole.In a most preferred embodiment, described lithium salts is lithium iodide.
In a preferred embodiment, described lithium salts is lithium iodide, and the molar concentration of described lithium iodide is for being no more than 1mol/L.
Lithium salts (as lithium iodide) can be dissolved in above-mentioned organic solvent formed battery 1 the electrolyte 7 that uses, the electrolyte formed has the conductivity (or being not less than the resistivity of 154 Ω cm) being not more than 6.5mS/cm.As concrete compound method, first can mix 1,2-dimethoxy-ethane and 1,3-dioxolane, then by the volume feed of (0-5]: [95-100), gamma-butyrolacton be added wherein, then toward wherein slowly adding lithium iodide, to guarantee to dissolve completely; Or by above-mentioned raw materials volume ratio, three kinds of solvents are mixed simultaneously, then slowly add lithium iodide.No matter with which kind of method mix, as long as the initial volume of solvent is than in above-mentioned scope, and conductivity is in above-mentioned scope, can obtain the electrolyte being applicable to lithium Fe battery of the present invention.Battery obtained by this electrolyte all can obtain technique effect of the present invention, therefore all within protection scope of the present invention.
Preferably, described organic electrolyte can have the conductivity of 2.0mS/cm to 6.5mS/cm, to guarantee the discharge performance of battery;
Further preferably, described organic electrolyte can have the conductivity of 4.0mS/cm to 5.5mS/cm, so that while guaranteeing fail safe, obtains good discharge performance.
The present invention is not to being limited as percentage by weight (wt.%) or molar concentration etc. as lithium iodide concentrations of the solute in electrolyte 7, because being weight percentage or molar concentration just one of factor affecting conductivity, be not enough to determine this conductivity, be also not enough to illustrate that the present inventor is for the special discovery solving battery of lithium-iron disulphide safety problem.The conductivity of electrolyte is not only by the impact of solute lithium salt as percentage by weight or molar concentration, also closely bound up with type of solvent, solute solubility in a solvent, extent of dissociation, solvation degree, electrolyte viscosity etc.Even if having selected percentage by weight, the conductivity of electrolyte also can be different because solvent composition is different.In any case, to achieve the object of the present invention, comprehensive above technical parameter and actual result, in order to improve fail safe further, and improving discharge performance, this electrolyte preferably has the conductivity of 2.0mS/cm to 6.5mS/cm, most preferably has the conductivity of 4.0mS/cm to 5.5mS/cm.
Described conductivity uses the Seven Multi conductivity measurement instrument of METTLER TOLEDO company to carry out, and test port is In-Lab Science, tests obtaining under the condition of 21+/-2C.
The present inventor is by research, and the mechanism of burning occurs after being punctured under 50%DOD state profound understanding battery of lithium-iron disulphide, have employed unique resolving ideas.Those skilled in the art know, and electrolyte needs to have good ionic conductivity to ensure the normal work of battery, and for this reason, those skilled in the art spare no effort to pursue conductivity high as far as possible always.But based on the particularity of battery of lithium-iron disulphide, the present inventor is but surprised to find that, the fail safe of existing lithium Fe battery is not enough, has close ties with high conductivity.The present inventor finds further, when adopting specific solvent burden ratio, when namely adopting above-mentioned electrolyte system, while guaranteeing lithium Fe battery fail safe, can not reduce cell discharge performance.
Adopt above-mentioned electrolyte system why can improve the reason of battery security not clear at present, by inference, reason may be as follows: when battery is punctured and forms internal short-circuit under 50%DOD state, to vigorous reaction be there is in battery of lithium-iron disulphide, battery temperature is made sharply to increase, this reaction acutely generally can end in about about 1.5 minutes, battery temperature just can decline afterwards, but because temperature is increased on electrolyte boiling point within short a few minutes, electrolyte solvent will sharply volatilize, thus form potential safety hazard.But in the present invention, this battery, by selecting suitable electrolytic conductivity scope, both slow down the speed of cell reaction when piercing through, and delayed the rising of battery temperature, in turn ensure that discharge performance not by appreciable impact.On the other hand, select the incompatible preparation electrolyte of above-mentioned group of solvents, the boiling point of electrolyte may be also improved, reducing the volatilization of electrolyte when heating up, also contributing to improving fail safe further.
As long as it should be noted that and adopt above-mentioned electrolyte system, lithium Fe battery of the present invention can also adopt other known preparation methods to make, and its preparation method does not form the restriction to protection scope of the present invention.
Embodiment
The present invention is further illustrated by the following examples.It should be noted that these embodiments do not form limiting the scope of the invention.
Embodiment of the present invention battery used is AA type battery, and its preparation method is as follows:
Get FeS
2this material, as positive electrode active materials, mixes in following ratio with conductive agent, makes positive mix by powder (picking up from the Natural pyrite of Yunfu, guangdong Province):
FeS
2: 91 % by weight;
Graphite: 8 % by weight;
Acetylene black: 1 % by weight.
With an organic solvent binding agent is made bonding glue, wherein, binding agent is 3 % by weight polystyrene-ethylene/butylene-styrene block copolymer (SEBS, commodity are called Kraton G1651), organic solvent is the Shell A100 (aromatic hydrocarbon solvent) of Shell company production and the mixture of Shell OMS (isoparaffin), and its mixed proportion is 4:6(weight ratio).
Carry out stirring to make anode sizing agent after above-mentioned positive mix is mixed by the weight ratio of 2:1 with bonding glue, and this slurry is coated in as on the aluminium foil of plus plate current-collecting body, then the base material after coating is dried, roll-in, cut process, obtain positive plate, its length is 285mm, width is 41mm, and thickness is 0.2mm.Use lithium metal as negative plate, its length is 310mm, and width is 39mm, and thickness is 0.16mm; Then, respectively one end of positive pole, cathodal current lead-in wire is connected on positive plate and negative plate and forms anode structure and negative pole structure; Then, anode structure, negative pole structure and barrier film (Celgard 2400) superposed and form battery together with being wound on; Finally, battery is put into battery container, inject electrolyte, seal rear and carry out pre-arcing process.Then battery at least normal temperature storage 24 hours to wait for the stable of battery system.
The present invention carries out the security performance puncturing to weigh described battery under adopting 50%DOD state, calculate according to design capacity, according to the mode of 200mA continuous discharge with the depth of discharge reaching 50%, carries out puncture subsequently and tests.
According to SJ/T11170-1998, UL2054:1997, GB/T18287-2000, battery puncture test carries out under the ambient temperature of 20 DEG C ± 5 DEG C, the battery (contact of thermocouple is fixed on battery surface) being connected to thermocouple is placed in fume hood, pierce through the center of battery side with the high temperature resistant draw point of diameter 3-8mm with the speed of 10mm/s-40mm/s, and keep random time.Specific requirement is:
1, the high temperature resistant draw point of ф 3mm-ф 8mm, draw point is long: 10cm, at least runs through the length of 3 cells when ensureing experiment;
2, ensure that draw point runs through whole battery;
3, with the speed of 10-40mm/s;
4, run through (draw point need stop in the battery) from the direction perpendicular to battery pole plates;
5, penetrating force: 150-200KG;
6, box-type equipment device explosion-proof, fire prevention, anticorrosive, easy to clean.
Embodiment 1
Electrolyte quota is as follows: anhydrous for 490ml 1,2-dimethoxy-ethane and anhydrous 1, the 3-dioxolane of 490ml are equaled 1 composition mixed solvent according to volume ratio, and above-mentioned solvent all can obtain from Suzhou Nuo Laite Co., Ltd.Gamma-butyrolacton and anhydrous lithium iodide (LiI) are all from Huarong Co., Ltd of Zhangjiagang Cathay.Get above-mentioned mixed solvent and gamma-butyrolacton 20ml to mix in the container of 2000ml, then toward wherein adding anhydrous lithium iodide gradually, stirring, making it fully dissolve, obtaining conductivity is the electrolyte of 5.0mS/cm.Carry out in the process preparing above-mentioned electrolyte all reaches-40 DEG C drying room at dew point.
Get the electrolyte prepared and make AA type battery of lithium-iron disulphide according to above-mentioned battery preparation method, sample is designated as A1.
Embodiment 2
Method is identical with embodiment 1, and difference changes the addition of anhydrous lithium iodide to make the electrolyte that conductivity is 6.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A2.
Embodiment 3
Method is identical with embodiment 1, and difference changes the addition of anhydrous lithium iodide to make the electrolyte that conductivity is 6.5mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A3.
Embodiment 4
Method is identical with embodiment 1, and difference changes the addition of anhydrous lithium iodide to make the electrolyte that conductivity is 4.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A4.
Embodiment 5
Method is identical with embodiment 1, and difference changes the addition of anhydrous lithium iodide to make the electrolyte that conductivity is 3.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A5.
Embodiment 6
Method is identical with embodiment 1, and difference changes the addition of anhydrous lithium iodide to make the electrolyte that conductivity is 2.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A6.
Embodiment 7
Method is identical with embodiment 1, and difference changes the addition of anhydrous lithium iodide to make the electrolyte that conductivity is 1.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A7.
Embodiment 8
Method is identical with embodiment 1, difference gets 495ml anhydrous 1,2-dimethoxy-ethane and 495ml anhydrous 1, the mixed solvent (volume ratio 1:1) of 3-dioxolane and gamma-butyrolacton 10ml mix in the container of 2000ml, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A8.
Embodiment 9
Method is identical with embodiment 1, difference gets 497.5ml anhydrous 1,2-dimethoxy-ethane and 497.5ml anhydrous 1, the mixed solvent (volume ratio 1:1) of 3-dioxolane and gamma-butyrolacton 5ml mix in the container of 2000ml, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A9.
Embodiment 10
Method is identical with embodiment 1, difference gets 485m l anhydrous 1,2-dimethoxy-ethane and 485ml anhydrous 1, the mixed solvent (volume ratio 1:1) of 3-dioxolane and gamma-butyrolacton 30ml mix in the container of 2000ml, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A10.
Embodiment 11
Method is identical with embodiment 1, difference gets 480ml anhydrous 1,2-dimethoxy-ethane and 480ml anhydrous 1, the mixed solvent (volume ratio 1:1) of 3-dioxolane and gamma-butyrolacton 40ml mix in the container of 2000ml, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A11.
Embodiment 12
Method is identical with embodiment 1, difference is anhydrous 1,2-dimethoxy-ethane and anhydrous 1,3-dioxolane, according to volume ratio 0.75:1 mixing, maintains gamma-butyrolacton relative to 1,2-dimethoxy-ethane and 1, the volume feed 2:98 of 3-dioxolane total amount is constant, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A12.
Embodiment 13
Method is identical with embodiment 1, difference is anhydrous 1,2-dimethoxy-ethane and anhydrous 1,3-dioxolane equals 0.5:1 mixing according to volume ratio, maintains gamma-butyrolacton relative to 1,2-dimethoxy-ethane and 1, the volume feed 2:98 of 3-dioxolane total amount is constant, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A13.
Embodiment 14
Method is identical with embodiment 1, difference is anhydrous 1,2-dimethoxy-ethane and anhydrous 1,3-dioxolane equals 0.25:1 mixing according to volume ratio, maintains gamma-butyrolacton relative to 1,2-dimethoxy-ethane and 1, the volume feed 2:98 of 3-dioxolane total amount is constant, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A14.
Embodiment 15
Method is identical with embodiment 1, difference is anhydrous 1,2-dimethoxy-ethane and anhydrous 1,3-dioxolane equals 1.5:1 mixing according to volume ratio, maintains gamma-butyrolacton relative to 1,2-dimethoxy-ethane and 1, the volume feed 2:98 of 3-dioxolane total amount is constant, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A15.
Embodiment 16
Method is identical with embodiment 1, difference is anhydrous 1,2-dimethoxy-ethane and anhydrous 1,3-dioxolane equals 2.0:1 mixing according to volume ratio, maintains gamma-butyrolacton relative to 1,2-dimethoxy-ethane and 1, the volume feed 2:98 of 3-dioxolane total amount is constant, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A16.
Embodiment 17
Method is identical with embodiment 1, difference is anhydrous 1,2-dimethoxy-ethane and anhydrous 1,3-dioxolane equals 2.5:1 mixing according to volume ratio, maintains gamma-butyrolacton relative to 1,2-dimethoxy-ethane and 1, the volume feed 2:98 of 3-dioxolane total amount is constant, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A17.
Embodiment 18
Method is identical with embodiment 1, difference gets 475ml anhydrous 1,2-dimethoxy-ethane and 475ml anhydrous 1, the mixed solvent (volume ratio 1:1) of 3-dioxolane and gamma-butyrolacton 50ml mix in the container of 2000ml, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A18.
Comparative example 1
Method is identical with embodiment 1, difference be the addition of adjustment anhydrous lithium iodide to make the electrolyte that conductivity is 7.0mS/cm, make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as B1.
Comparative example 2
Method is identical with embodiment 1, difference be the addition of adjustment anhydrous lithium iodide to make the electrolyte that conductivity is 7.5mS/cm, make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as B2.
Comparative example 3
Method is identical with embodiment 1, and difference is not containing gamma-butyrolacton in electrolyte, and the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as B3.
Comparative example 4
Method is identical with embodiment 1, difference gets 470ml anhydrous 1,2-dimethoxy-ethane and 470ml anhydrous 1, the mixed solvent (volume ratio 1:1) of 3-dioxolane and gamma-butyrolacton 60ml mix in the container of 2000ml, the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 5.0mS/cm, make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as B4.
Comparative example 5
Method is identical with embodiment 1, and difference is not containing gamma-butyrolacton in electrolyte, and the addition of adjustment anhydrous lithium iodide is to make the electrolyte that conductivity is 8.0mS/cm, and make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as B5.
The battery of above-described embodiment and comparative example is carried out 50%DOD(see describing above), then carry out puncture experiment, observe the battery number whether battery burns and burning occurs, it is as follows that statistics lists table 1 in:
Table 1 battery of lithium-iron disulphide 50%DOD punctures experimental result
| Sample number | Puncture electric experimental cell sum/only | Fuel cell number/only |
| A1 | 150 | 0 |
| A2 | 150 | 0 |
| A3 | 150 | 3 |
| A4 | 150 | 0 |
| A5 | 150 | 0 |
| A6 | 150 | 0 |
| A7 | 150 | 0 |
| A8 | 150 | 0 |
| A9 | 150 | 5 |
| A10 | 150 | 0 |
| A11 | 150 | 2 |
| A12 | 150 | 0 |
| A13 | 150 | 0 |
| A14 | 150 | 0 |
| A15 | 150 | 0 |
| A16 | 150 | 0 |
| A17 | 150 | 0 |
| A18 | 150 | 5 |
| B1 | 150 | 17 |
| B2 | 150 | 59 |
| B3 | 150 | 10 |
| B4 | 150 | 24 |
| B5 | 150 | 128 |
As seen from the above table, when battery of the present invention is carried out puncture experiment time, battery can not burn substantially, even if or burn, quantity is also substantially controlled.When carrying out same experiment to the battery of comparative example, battery is easy to burn, and burning probability is higher.
Carry out discharge test to above-mentioned battery, often group test sample number is 5, and method of testing adopts continuous discharge, the discharge capacity of statistics battery.That is, cut-ff voltage 0.9V is discharged into the current continuity of battery applying 200mA.Result is added up in table 2:
Table 2 battery of lithium-iron disulphide 200mA continuous discharge result/by the end of 0.9V
As seen from the above table, the battery that embodiments of the invention obtain shows the performance no less than comparative example battery in the test of this discharge performance.
The present invention is illustrated by above-described embodiment, but should be understood that, above-described embodiment just for the object of illustrating and illustrate, and is not intended to the present invention to be limited in described scope of embodiments.In addition it will be appreciated by persons skilled in the art that the present invention is not limited to above-described embodiment, more kinds of variants and modifications can also be made according to instruction of the present invention, within these variants and modifications all drop on the present invention's scope required for protection.Protection scope of the present invention defined by the appended claims and equivalent scope thereof.
Claims (10)
1. a battery of lithium-iron disulphide, described battery: the negative pole be made up of lithium metal or its alloy, using ferrous disulfide as the positive pole of positive electrode active materials and organic electrolyte, be provided with barrier film between described negative pole and positive pole; It is characterized in that:
Described organic electrolyte has the conductivity being not more than 6.5mS/cm; And
Described organic electrolyte comprises organic solvent and is dissolved in lithium salts wherein, described organic solvent is by gamma-butyrolacton, 1,2-dimethoxy-ethane and 1,3-dioxolane forms, wherein, gamma-butyrolacton is (0-5]: [95-100) relative to the volume feed of 1,2-dimethoxy-ethane and 1,3-dioxolane total amount.
2. battery of lithium-iron disulphide according to claim 1, wherein, described organic electrolyte has the conductivity of 2.0mS/cm to 6.5mS/cm.
3. battery of lithium-iron disulphide according to claim 2, wherein, described organic electrolyte has the conductivity of 4.0mS/cm to 5.5mS/cm.
4. battery of lithium-iron disulphide according to claim 1, described lithium salts is selected from LiTFS, LiTFSI, LiI, LiBr, LiBF
4, LiClO
4and LiPF
6in one or more.
5. battery of lithium-iron disulphide according to claim 1, described lithium salts comprises the LiI of more than 90 % by mole.
6. battery of lithium-iron disulphide according to claim 1, described lithium salts is LiI.
7. battery of lithium-iron disulphide according to claim 1, wherein, described volume feed is [0.5-5]: [95-99.5].
8. battery of lithium-iron disulphide according to claim 1, wherein, described volume feed is [1.5-3]: [97-98.5].
9. battery of lithium-iron disulphide according to claim 1, wherein, the volume feed of 1,2-dimethoxy-ethane and 1,3-dioxolane is [0.25-2]: 1.
10. battery of lithium-iron disulphide according to claim 1, wherein, the volume feed of 1,2-dimethoxy-ethane and 1,3-dioxolane is [0.5-1]: 1.
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| CN102318113A (en) * | 2009-02-12 | 2012-01-11 | 吉列公司 | Lithium cell with iron disulfide cathode |
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| KR100472509B1 (en) * | 2002-10-04 | 2005-03-10 | 삼성에스디아이 주식회사 | Organic electrolytic solution and lithium battery employing the same |
| US7785740B2 (en) * | 2004-04-09 | 2010-08-31 | Air Products And Chemicals, Inc. | Overcharge protection for electrochemical cells |
| GB0808059D0 (en) * | 2008-05-02 | 2008-06-11 | Oxis Energy Ltd | Rechargeable battery with negative lithium electrode |
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| CN102318113A (en) * | 2009-02-12 | 2012-01-11 | 吉列公司 | Lithium cell with iron disulfide cathode |
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