CN102790235A - Lithium-iron disulfide battery - Google Patents
Lithium-iron disulfide battery Download PDFInfo
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- CN102790235A CN102790235A CN2012102951407A CN201210295140A CN102790235A CN 102790235 A CN102790235 A CN 102790235A CN 2012102951407 A CN2012102951407 A CN 2012102951407A CN 201210295140 A CN201210295140 A CN 201210295140A CN 102790235 A CN102790235 A CN 102790235A
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- iron disulphide
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Abstract
The invention discloses a lithium-iron disulfide battery which comprises a cathode, an anode and organic electrolyte. The cathode is made of metallic lithium or alloy thereof, the anode uses iron disulfide as anode active materials, and diaphragms are arranged between the cathode and the anode. The lithium-iron disulfide battery is characterized in that the organic electrolyte has conductivity ranging from 6.5mS/cm to 8.0mS/cm and comprises organic solvent and lithium salt dissolved in the organic solvent, the organic solvent is composed of gamma-butyrolactone, 1,2-dimethoxyethane and 1,3-dioxolane, the raw material volume ratio of the gamma-butyrolactone to total quantity of the 1,2-dimethoxyethane and the 1,3-dioxolane is (0-5):(95-100), and the diaphragms are polyethylene microporous diaphragms.
Description
Technical field
The present invention relates to the 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 has received more and more people's concern and attention owing to have advantages such as energy density height, voltage is high, operating temperature range is wide, the life-span is long.In more than ten years in the past, lithium battery once having occupied leading position in (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 anodal (positive pole) active material with the ferrous disulfide, be negative pole (negative pole) active material with the lithium metal and be the battery of electrolyte with the organic electrolyte.Therefore the voltage of this primary cell can reach 1.5V, can substitute alkaline battery commonly used now and uses as the portable energy source of ordinary consumption electronic equipment.In addition, this primary cell also has the specific discharge capacity more much higher than alkaline battery, and cryogenic property is good, in light weight, so it is as the high-power battery of a new generation, just more and more receives people's welcome, and market prospects are boundless.
Yet things all has dual character, and its advantage tends to become shortcoming under a stable condition.This just needs people to go balance relation wherein, brings into play its biggest advantage as far as possible and overcomes its shortcoming.The battery of lithium-iron disulphide of as above addressing has very high energy, and people have only release through its energy there being control to reach the application target of expection.On the contrary, out of control if energy discharges, will bring people do not hope the result that takes place to 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 (like burning, blast etc.) is of common occurrence.Again and again incident makes lithium battery safety problem alarm bell Chang Ming.Each producer is directed against this problem one after another and launches further investigation and inquire into, and through carrying out methods such as battery structure optimization, increase safety guard, strict control technology, reduces the risk that safety problem takes place, and has obtained effective progress.Like being widely used of temperature-sensitive element (PTC), all confidence is provided for the good lithium battery of the relieved use of people to prevent the blast problem that battery is caused to prevent that cell internal pressure is excessive by the use of outside short circuit, cell safety valve and effectively to control the inside battery moisture to prevent the technical measures such as combine of water and lithium metal.
Battery of lithium-iron disulphide is as the lithium battery of emerging kind, just by positive regard.Even existing related specy battery such as research and development experiences such as lithium-manganese dioxide battery and lithium ion battery are still not enough to the research of battery of lithium-iron disulphide fail safe aspect.Present research turns one's attention to the discharge performance that how to improve battery greatly at most, improve the storage life of battery and about on the manufacturing process of battery or the like the problem.The battery of lithium-iron disulphide that how to obtain high power capacity all is provided like patent 200580044452.9,200480034479.5,200580044588.X; Patent 200880008965.8,201110031246.1 has been paid close attention to the problem of pretreatment of battery with increase battery storage performance, and patent 200810016797.9,200910020280.1,200910037961.9 etc. have all related to the manufacturing process of battery of lithium-iron disulphide.Seldom have and relate to the problem that solves the battery of lithium-iron disulphide fail safe with new thinking.
The fail safe of battery of lithium-iron disulphide is among each links such as manufacturing, storage, transportation, use and waste disposal of battery.For work such as manufacturing, transportation and storages, generally all is to have the producer of specialty to carry out, through the control of technology effectively being prevented the generation of safety problem, but battery finally is to transfer to non-professional terminal use to use.Normally use (discharge) and general routine misuse for battery, prior art has had related.To lithium battery safety problem control and the various standards such as UN/DOT 38.3, ANSI C18.3, IEC 60086-4 and the UL1642 that carry out, need transportation, user's abuse to lithium battery like overdischarge, charging, external short circuit, fall, problem such as vibrations control effectively.Battery of lithium-iron disulphide for high energy; The general packaging structure (like the shell of hard steel) that adopts close and firm to prevent the user because curiosity or other reasons and battery is opened; Yet desired user uses in strict accordance with the use indication of battery manufacturer and does not abuse just and be based on one's own wishful thinking.The short circuit meeting of high energy battery of lithium-iron disulphide forms the rapid release to the energy content of battery.But; Outside conventional just-the negative pole short circuit can be able to through the temperature-sensitive element (PTC) that positive temperature coefficient is set in battery structure (circuit) control; This is because when battery generation external short circuit; Greatly electric current produces great amount of heat battery temperature is raise through cell circuit, and the temperature-sensitive element of positive temperature coefficient (PTC) thus resistance can increase rapidly at a certain temperature entire circuit is broken off; Cell reaction stopped, guaranteed the externally safety under the short-circuit conditions of battery.Yet the inside positive and negative electrode that causes if battery generation internal short-circuit such as inside battery barrier film go wrong directly links to each other, perhaps battery pushed or by situation such as the metal spicule run through under, the temperature-sensitive element of positive temperature coefficient is powerless.Existing battery of lithium-iron disulphide technology is not also shown great attention to this, and one of reason is this situation and comes so obviously unlike other safety problem.In addition, in some cases, have defective or suffer whole slight extruding like the inside battery barrier film, even if the short circuit problem of inside battery has taken place, what battery also can not show so is irremediable until the incident that takes place like burning or blast.Usually accepted with the notion of " self-discharge of battery " by people in this case.Problem is, battery is thrown in much complicated than our imagination of situation behind the market, and we have to expect the problem that battery takes place suffering under extremely abominable the treating.The danger of combustion that possibly cause can cause very big threat to an innocent person's the person and property safety, moreover the burning of lithium battery is not just can simply put out through water, and such problem will seriously be destroyed the trust of consumer to it.
Therefore, need a kind of lithium Fe battery at present badly, this lithium Fe battery should still be guaranteed certain fail safe under above-mentioned extreme case, possesses simultaneously discharge performance preferably again, satisfying the needs in market, and meets supervision standard.
Summary of the invention
In the summary of the invention part, introduced the notion of a series of reduced forms, this will further explain in the embodiment part.Summary of the invention part of the present invention does not also mean that key feature and the essential features that will attempt to limit technical scheme required for protection, does not more mean that the protection range of attempting to confirm technical scheme required for protection.
Based on above technical problem; The invention provides a kind of safe battery of lithium-iron disulphide; Even this battery suffer abominable internal short-circuit like the situation that is run through (below be called puncture) by the metal spicule under; Still be difficult to burn, and guarantee discharge performance preferably, thereby accomplished the present invention.
The invention provides a kind of battery of lithium-iron disulphide, said battery comprises: the negative pole of being processed by lithium metal or its alloy, with positive pole and the organic electrolyte of ferrous disulfide as positive electrode active materials is provided with barrier film between said negative pole and the positive pole; It is characterized in that: said organic electrolyte has the conductivity of 6.5mS/cm to 8.0mS/cm; Said organic electrolyte comprises organic solvent and is dissolved in lithium salts wherein; Said organic solvent is by gamma-butyrolacton, 1,2-dimethoxy-ethane and 1, and the 3-dioxolane is formed; Wherein, Gamma-butyrolacton is with respect to 1,2-dimethoxy-ethane and 1, and the volume feed of 3-dioxolane total amount is (0-5]: [95-100); Said barrier film is the little porous septum of polyethylene.
Battery of lithium-iron disulphide of the present invention has excellent security, even under extreme case, also be difficult to blast or explode, and has good discharge performance, thereby has extensive market prospects, can make lithium Fe battery satisfy commercial actual demand.
Description of drawings
Fig. 1 is the structure longitudinal section of lithium Fe battery of the present invention.
Embodiment
In the description hereinafter, a large amount of concrete details have been provided so that more thorough understanding of the invention is provided.Yet, it will be apparent to one skilled in the art that the present invention can need not one or more these details and be able to enforcement.In other example,, describe for technical characterictics more well known in the art for fear of obscuring with the present invention.
Referring to 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: the slurry that will contain ferrous disulfide (positive electrode active materials) is coated on the plus plate current-collecting body; Cut; Make positive plate 2, negative plate 4, the barrier film of processing with positive plate 2, barrier film 3, by lithium metal or its alloy then 3 is range upon range of together and reel and form electric core (for example cylindrical electric core), and electric core is put into battery container 5; Injection organic electrolyte 7 also seals, and promptly makes finished product battery (or claiming " new battery " or " new system battery ").Wherein also can comprise the positive and negative electrode terminal of respectively electric current being guided to battery with anodal current feed 8 and cathodal current lead-in wire 6.The temperature-sensitive element 9 and the explosion-proof sheet metal 10 that is provided with pressure switch that in the hermetically-sealed construction of battery, also can comprise alternatively, positive temperature coefficient.
Positive plate 2 has comprised the anode sizing agent on plus plate current-collecting body and at least one side that is coated in plus plate current-collecting body.Wherein, the anode sizing agent of battery of lithium-iron disulphide generally comprises anodal solid material, binding agent and solvent, and anodal solid material generally comprises the ferrous disulfide (FeS as positive electrode active materials
2) and conductive agent.Positive electrode active materials also can contain just like FeS, CoS
2, NiS
2Deng the 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 for use like crystal structure type, conduction type and particle size distribution etc. of material, those skilled in the art can select according to the hope technique effect that reaches.
Above-mentioned conductive agent is used to strengthen the electron conduction of positive plate 2, typically can use graphite (natural perhaps manual work), acetylene black, carbon black or its mixture.Its content in the solid material of anode sizing agent can be 1 weight %-15 weight %, and this ratio can guarantee that positive plate has enough electron conductions to be unlikely to again to take the space of too many positive electrode active materials and influences battery performance.The producer of conductive agent can at home and abroad all can find, as can be from TIMICAL or Shaowu, Fujian graphite factory etc.
Positive plate 2 uses binding agents, and purpose is to make positive electrode active materials adhere on the described plus plate current-collecting body and guarantees that positive electrode active materials on the positive plate after dry is unlikely to come off and influences battery performance.Binding agent generally uses high molecular polymer, and high molecular polymer is dissolved in the solvent and forms the bonding glue with certain viscosity, can supply to be coated on the anode sizing agent on the plus plate current-collecting body to form with positive electrode active materials and conductive agent.There are two kinds of comparatively ripe systems available at present.One of which for use as from SEBS (polystyrene-ethylene/butylene-styrene block copolymer) binding agent of Kraton with for example from the Shell A100 (aromatic hydrocarbon solvent) of Shell company with Shell OMS (isoparaffin) the formation glue that bonds; It is two for using PVDF (Kynoar) and NMP (N-methyl pyrrolidone) to form the glue that bonds.Wherein, the ratio of binding agent in said glue can be 5 weight % or higher.Based on mentioned component and proportion, those skilled in the art can be according to actual needs with viscosity adjustment to the desirable scope of anode sizing agent so that the carrying out of coating processes.Additionally, also can adopt one or more binding agents as required and simultaneously, as long as can reach above-mentioned purpose.
Employed plus plate current-collecting body in the positive plate 2; Generally can form by one or more metals; It is shaped as paillon foil or netted, and material can be aluminium, nickel, stainless steel etc., all can like the stainless (steel) wire that can use lithium ion battery aluminium foil commonly used or lithium-manganese dioxide battery to use.Thickness is generally 20 microns even can more approach as 15 microns, thinks that battery active material provides more space and increases battery performance.
The manufacture process of positive plate 2 is generally following: at first with active material FeS
2Powder mixes with conductive agent graphite, acetylene black, forms positive powder, and binding agent is mixed with organic solvent and forms glue.Then positive powder and glue are mixed together the anode sizing agent that formation can supply apply.Adopt transfer type or roller coat formula evenly to be coated in slurry on the plus plate current-collecting body, carry out drying and remove organic solvent wherein, form dry positive pole, carry out roll-in again, cut into needed size at last to certain thickness.Thereby form positive plate 2.
Generally speaking, the manufacturing of positive plate 2 can adopt the method for lithium Fe battery known to carry out, and ratio that more than provides and composition can not be regarded as the restriction to protection range of the present invention.
Negative plate 4 in the battery 1; Its active material is lithium metal Li; Can use pure metal lithium, the intensity of alloy that also can use lithium metal and other metals such as aluminium to form to obtain to be fit to, its shape is preferably the paper tinsel shape; Thickness can basis with anodal relative area on the capacity of the active material principle of mating confirm, be generally about 0.15mm between the 0.25mm.Length and width can be confirmed according to battery design and with the relation of anodal size.
The effect of barrier film 3 is to provide the passage of inside battery ion migration, isolates directly electrically contacting to prevent battery generation internal short-circuit between positive pole and the negative pole.The inventor is surprised to find that; Select for use specific barrier film safeguard protection to be provided for the unusual inner/outer short circuit of battery; Also promptly, when adopting the little porous material of polythene PE as barrier film, the fail safe of battery that use is had the electrolyte of high conductivity has further improvement effect.The micro-porous film of described barrier film for adopting the polythene PE material to process, thickness is preferably the 15-35 micron.Further, the thickness of described barrier film 20-25 micron more preferably.The instance of said barrier film has the PE barrier film produced from company of Asahi Chemical Industry (for example, model is the barrier film of COD-120,20 microns of thickness, air permeability 240sec/100ml, porosity 45%, closed pore temperature (shutdown temperature) is less than 150 ℃).In addition, also can adopt the UBE barrier film of close barrier film of performance such as Ube.Find also that further when adopting closed pore temperature smaller or equal to 150 ℃ PE barrier film, the fail safe of battery has more significantly and improves.Therefore, among the present invention, preferably adopt closed pore temperature smaller or equal to 150 ℃ PE barrier film barrier film as above-mentioned lithium Fe battery.
Except above-mentioned execution mode, battery of the present invention also can adopt the basic structure of known conventional battery of lithium-iron disulphide, for example the battery structure of CN101361215A proposition.Except cylindrical battery shown in Figure 1, can also adopt battery configuration such as button, monetary apparatus, battery configuration does not constitute the restriction to protection range of the present invention.
The good safety that the present invention is alleged is meant according to lithium battery safety standard SJ/T11170-1998, UL2054:1997, GB/T18287-2000 and the security test of carrying out.Concrete detection method and requirement will be described in an embodiment.In brief, of " background technology " part, be meant that battery still possesses certain fail safe receiving under abominable inside puncture (internal short-circuit) situation.The present invention has realized the safety of battery under the puncture situation through to the specific electrolyte composition and the selection of the combination of diaphragm material, has strengthened the tolerance of battery to adverse circumstances.
Lithium-iron disulfide is compared with other batteries, has certain particularity.When battery operated, following chemical reaction takes place:
FeS
2+4Li—>Fe+2Li
2S （1）
In fact, under the situation of middle low discharging current, this chemical reaction is divided into two steps to be accomplished:
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 after the iron in the ferrous disulfide is reduced into to fe Fe, because the fe granularity that is reduced out is less; Activity is extremely strong, has increased the conductivity of positive plate greatly.Inventor's research of the present invention shows that battery is in the most unsafe stage when having fe to exist, and after battery was finished using, because the energy content of battery has exhausted basically, battery transferred safety to.For this reason; Inventor's establishing criteria SJ/T11170-1998, UL2054:1997, GB/T18287-2000; And calculate the time that produces fe when lithium-iron disulfide reacts, be approximately 50% of battery consumption design capacity, i.e. 50% depth of discharge (Depth of Discharge; Abbreviation DOD), represent that with 50%DOD battery uses to the state of design capacity one half below.Among the present invention, under the 50%DOD state, carry out battery puncture experiment, with the validity of explanation the present invention for solution battery of lithium-iron disulphide safety problem.
The user is after obtaining battery of lithium-iron disulphide; Usually can not once battery be used up, but use off and on, promptly battery might be in any state of 0%DOD to 100%DOD; Draw through experimental summary and theory analysis, the precarious position when battery reaches 50%DOD is representative.
For reaching effect of the present invention, the electrolyte 7 that battery 1 uses has comprised organic solvent and has been 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) with 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, the 3-dioxolane is formed, wherein; Gamma-butyrolacton is with respect to 1; 2-dimethoxy-ethane and 1, the volume feed of 3-dioxolane total amount is (0-5]: [95-100) (volume that is the former is for greater than 0 and smaller or equal to 5 parts, and the latter's volume is more than or equal to 95 parts and less than 100 parts).
Preferably, the above-mentioned raw materials volume ratio can be [0.5-5]: [95-99.5].
More preferably, the above-mentioned raw materials volume ratio can be [1.5-3]: [97-98.5], and to improve the fail safe of battery as much as possible.
Wherein, 1,2-dimethoxy-ethane and 1, the volume feed of 3-dioxolane can be 0.25-2:1.
Preferably, 1,2-dimethoxy-ethane and 1, the volume feed of 3-dioxolane can be 0.5-1:1, to guarantee electrolyte flow property, makes lithium salts that disassociation preferably can be arranged simultaneously again.
Typically, said 1,2-dimethoxy-ethane and 1, the volume feed of 3-dioxolane can be about 1:1.In addition, also can in above-mentioned scope, adjust according to the factors such as cost of material.More than various proportions all can realize basic effect of the present invention.The present invention does not attempt its ratio is carried out the strictness restriction.
" volume feed " of indication of the present invention is meant at normal temperatures the volume ratio of two or more raw materials before mixing that is used to mix, and wherein " volume " that be used to compare of indication is the initial volume before mixing.Wherein, " gamma-butyrolacton with respect to 1,2-dimethoxy-ethane and 1; volume feed of 3-dioxolane total amount " is meant that the volume of gamma-butyrolacton before mixing is with respect to 1; The volume ratio at normal temperatures of 2-dimethoxy-ethane and 1,3-dioxolane initial volume sum separately, " 1; 2-dimethoxy-ethane and 1, the volume feed of 3-dioxolane " are meant at normal temperatures the volume ratio of these two kinds of solvents before mixing.
Comprised lithium salts in the electrolyte 7, said lithium salts can be from lithium salts such as LiTFS (trifluoromethyl sulfonic acid lithium), LiTFSI (two (fluoroform sulphonyl) imines lithium), LiI, LiBr, LiBF
4, LiClO
4And LiPF
6In select one or more for use, wherein, lithium iodide (LiI) preferably comprises, more preferably this lithium salts comprises the above lithium iodide of 90 moles of %.In a most preferred embodiment, said lithium salts is a lithium iodide.
In a preferred embodiment, said lithium salts is a lithium iodide, and the molar concentration of said lithium iodide is for being no more than 1mol/L.
Can lithium salts (like lithium iodide) is dissolved in the above-mentioned organic solvent and form battery 1 employed electrolyte 7, the conductivity that formed electrolyte has 6.5mS/cm-8.0mS/cm gets final product.As concrete compound method, can mix 1 earlier, 2-dimethoxy-ethane and 1, the 3-dioxolane, the volume feed by (0-5]: [95-100) adds gamma-butyrolacton wherein again, then toward wherein slowly adding lithium iodide, to guarantee that dissolving is fully; Perhaps three kinds of solvents are mixed simultaneously, slowly add lithium iodide then by the above-mentioned raw materials volume ratio.No matter with which kind of method mix, the initial volume that needs only solvent is than in above-mentioned scope, and conductivity can obtain to be applicable to the electrolyte of lithium Fe battery of the present invention in above-mentioned scope.All can obtain technique effect of the present invention by the prepared battery of this electrolyte, therefore all within protection scope of the present invention.
Preferably, said organic electrolyte can have the conductivity of 6.5mS/cm to 7.5mS/cm, to guarantee the discharge performance of battery;
Further preferably, said organic electrolyte can have the conductivity of 7.0mS/cm to 7.5mS/cm, so that when guaranteeing fail safe, obtains good discharge performance.
The present invention is limiting like percentage by weight (wt.%) or molar concentration etc. the solute concentration in the electrolyte 7 (like lithium iodide concentration) not; Because percentage by weight or molar concentration just influence one of factor of conductivity; Be not enough to confirm this conductivity, be not enough to also explain that the inventor is for the special discovery that solves the battery of lithium-iron disulphide safety problem.The conductivity of electrolyte not only receives the influence of solute lithium salt such as percentage by weight or molar concentration, and is also closely bound up with solubility in solvent of type of solvent, solute, extent of dissociation, solvation degree, electrolyte viscosity etc.Even selected percentage by weight, the conductivity of electrolyte also can be different because of solvent composition.In any case, for reaching the object of the invention, comprehensive above technical parameter and actual result, for further raising fail safe and discharge performance, electrolyte most preferably has the conductivity of 7.0mS/cm to 7.5mS/cm.
Described conductivity uses the Seven Multi conductivity measurement instrument of METTLER TOLEDO company to carry out, and test port is In-Lab Science, 21+/-test obtaining under the condition of 2C.
Among the present invention, the inventor is through research, and the profound understanding battery of lithium-iron disulphide receives the mechanism that burning takes place in the back of puncturing under the 50%DOD state, adopted unique solution thinking.Those skilled in the art know, and electrolyte need have good ionic conductivity to guarantee the operate as normal of battery, and for this reason, those skilled in the art spare no effort to pursue high as far as possible conductivity always.But based on the particularity of battery of lithium-iron disulphide, the inventor is surprised to find that but the fail safe of existing lithium Fe battery is not enough, with high conductivity close ties is arranged.The inventor further finds, when adopting specific solvent burden ratio promptly to adopt above-mentioned electrolyte system, if adopt specific diaphragm material, then can when guaranteeing the lithium Fe battery fail safe, also can make the discharge performance of battery unaffected basically.
It is not clear at present to adopt the combination of above-mentioned electrolyte system and diaphragm material why can improve the reason of battery security; By inference, reason maybe be as follows: common batteries is punctured under the 50%DOD state and when forming internal short-circuit, vigorous reaction will take place battery of lithium-iron disulphide; Battery temperature is sharply risen; This violent reaction generally can be end in about about 1.5 minutes, and battery temperature just can descend afterwards, but owing to temperature is being increased within short a few minutes on the electrolyte boiling point; Electrolyte solvent will sharply volatilize, thereby form potential safety hazard.Among the present invention, select the incompatible preparing electrolyte of above-mentioned group of solvents for use, can improve the boiling point of electrolyte, reduce the volatilization of electrolyte when heating up, thereby improve fail safe.Meanwhile; It is the microporous polyethylene film material that the present invention has also selected specific diaphragm material for use; Because the closed temperature (for example about 130 ℃) of this material is lower; Closure possibly taken place by hole of being penetrated in it in above-mentioned temperature-rise period, thereby cuts off electric current, guarantees thus that battery temperature is unlikely to rise to battery is burnt.
It should be noted that lithium Fe battery of the present invention can also adopt other known preparation methods to process as long as adopt above-mentioned electrolyte system, its preparation method does not constitute the restriction to protection scope of the present invention.
Embodiment
Below through embodiment the present invention is further described.It should be noted that these embodiment do not constitute the restriction to protection range of the present invention.
The used battery of the embodiment of the invention is AA type battery, and its preparation method is following:
Get FeS
2Powder (picking up from the natural pyrite of Yunfu, Guangdong) is pressed following mixed as positive electrode active materials with this material and conductive agent, processes positive mix:
FeS
2: 91 weight %;
Graphite: 8 weight %;
Acetylene black: 1 weight %.
With an organic solvent binding agent is processed the bonding glue; Wherein, Binding agent is 3 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), its mixed proportion is 4:6 (weight ratio).
Above-mentioned positive mix is stirred to process anode sizing agent after mixing by the weight ratio of 2:1 with the bonding glue; And this slurry is coated on the aluminium foil as plus plate current-collecting body; Then the base material after applying is dried, roll-in, cut processing, 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 an end anodal, the cathodal current lead-in wire is connected to positive electrode structure of formation and negative pole structure on positive plate and the negative plate; Then, with positive electrode structure, negative pole structure and barrier film stack and be wound on and form battery together; At last, battery is put into battery container, inject electrolyte, seal the back and carry out the pre-arcing processing.Then battery at least normal temperature storage 24 hours to wait for the stable of battery system.
The present invention adopts to puncture under the 50%DOD state and weighs the security performance of said battery, calculate according to design capacity, according to the mode of 200mA continuous discharge to reach 50% depth of discharge, the experiment of puncturing subsequently.
According to SJ/T11170-1998, UL2054:1997, GB/T18287-2000; Battery puncture test is carried out under 20 ℃ ± 5 ℃ ambient temperature; The battery that is connected to thermocouple (contact of thermocouple is fixed on the battery surface) is placed fume hood; High temperature resistant draw point with diameter 3-8mm pierces through the center of battery side with the speed of 10mm/s-40mm/s, and keeps random time.Specific requirement is:
1, the high temperature resistant draw point of ф 3mm-ф 8mm, draw point is long: 10cm, assurance runs through the length of 3 cells at least when testing;
2, guarantee that draw point runs through entire cell;
3, with the speed of 10-40mm/s;
4, run through (draw point need rest on the battery) from direction perpendicular to battery pole plates;
5, penetrating force: 150-200KG;
6, explosion-proof, the fire prevention of box-type equipment device, anticorrosive, easy to clean.
Embodiment 1
Electrolyte quota is following: 490ml is anhydrous 1, and 2-dimethoxy-ethane and 490ml are anhydrous 1, and the 3-dioxolane equals 1 according to volume ratio and forms mixed solvent, and above-mentioned solvent all can the peculiar limit of promise Lay company obtain from Suzhou.Gamma-butyrolacton and anhydrous lithium iodide (LiI) are all from Zhangjiagang Cathay China Ei Co., Ltd..Get above-mentioned mixed solvent and gamma-butyrolacton 20ml and in volume is the container of 2000ml, mix, toward wherein adding anhydrous lithium iodide gradually, stir then, it is fully dissolved, obtaining conductivity is the electrolyte of 7.5mS/cm.The process of preparing above-mentioned electrolyte all reaches in dew point-40 ℃ the drying room carries out.
With the electrolyte for preparing as electrolyte; And be that 20 microns microporous polyethylene film (model is COD-120, is produced by company of Asahi Chemical Industry, and closed pore temperature is 145 ℃) is as barrier film with thickness; 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 different is to change the addition of anhydrous lithium iodide to make the electrolyte that conductivity is 6.5mS/cm, makes AA type battery of lithium-iron disulphide with this electrolyte, and sample is designated as A2.
Embodiment 3
Method is identical with embodiment 1, and different is to change the addition of anhydrous lithium iodide to make the electrolyte that conductivity is 8.0mS/cm, makes AA type battery of lithium-iron disulphide with this electrolyte, and sample is designated as A3.
Embodiment 4
Method is identical with embodiment 1, and different is, and to adopt thickness be that as the barrier film manufacture batteries, sample is designated as A4 for 25 microns microporous polyethylene film (model is COD-120, is produced by company of Asahi Chemical Industry, and closed pore temperature is 145 ℃).
Method is identical with embodiment 1, and different is, and to adopt thickness be that as the barrier film manufacture batteries, sample is designated as A5 for 30 microns microporous polyethylene film (model is COD-120, is produced by company of Asahi Chemical Industry, and closed pore temperature is 145 ℃).
Method is identical with embodiment 1; It is anhydrous 1 with 495ml that different is, 2-dimethoxy-ethane and 495ml are anhydrous 1, and the 3-dioxolane is formed mixed solvent according to volume ratio 1:1; Mix in volume is the container of 2000ml with gamma-butyrolacton 10ml then; The addition of adjustment anhydrous lithium iodide is made AA type battery of lithium-iron disulphide to configure the electrolyte that conductivity is 7.5mS/cm with this electrolyte, and sample is designated as A6.
Method is identical with embodiment 1; Different is to get 497.5ml anhydrous 1; 2-dimethoxy-ethane and 497.5ml are anhydrous 1, and the mixed solvent of 3-dioxolane (volume ratio 1:1) and gamma-butyrolacton 5ml mix in volume is the container of 2000ml, and the addition of adjustment anhydrous lithium iodide is to configure the electrolyte that conductivity is 7.5mS/cm; Make AA type battery of lithium-iron disulphide with this electrolyte, sample is designated as A7.
Method is identical with embodiment 1; Different is to get 485ml anhydrous 1; 2-dimethoxy-ethane and 485ml are anhydrous 1, and the mixed solvent of 3-dioxolane (volume ratio 1:1) and gamma-butyrolacton 30ml mix in volume is the container of 2000ml, and the addition of adjustment anhydrous lithium iodide is 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 A8.
Method is identical with embodiment 1; Different is to get 480ml anhydrous 1; 2-dimethoxy-ethane and 480ml are anhydrous 1, and the mixed solvent of 3-dioxolane (volume ratio 1:1) and gamma-butyrolacton 40ml mix in volume is the container of 2000ml, and the addition of adjustment anhydrous lithium iodide is 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 A9.
Method is identical with embodiment 1; Different is to get 475ml anhydrous 1; 2-dimethoxy-ethane and 475ml are anhydrous 1, and the mixed solvent of 3-dioxolane (volume ratio 1:1) and gamma-butyrolacton 50ml mix in volume is the container of 2000ml, and the addition of adjustment anhydrous lithium iodide is 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 A10.
Embodiment 11
Method is identical with embodiment 1, and it is anhydrous 1 that different is, 2-dimethoxy-ethane and anhydrous 1; The 3-dioxolane mixes according to volume ratio 0.75:1, keeps gamma-butyrolacton with respect 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 made AA type battery of lithium-iron disulphide to make the electrolyte that conductivity is 7.5mS/cm with this electrolyte, and sample is designated as A11.
Embodiment 12
Method is identical with embodiment 1, and it is anhydrous 1 that different is, 2-dimethoxy-ethane and anhydrous 1; The 3-dioxolane equals 0.5:1 according to volume ratio to be mixed, and keeps gamma-butyrolacton with respect 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 made AA type battery of lithium-iron disulphide to make the electrolyte that conductivity is 7.5mS/cm with this electrolyte, and sample is designated as A12.
Embodiment 13
Method is identical with embodiment 1, and it is anhydrous 1 that different is, 2-dimethoxy-ethane and anhydrous 1; The 3-dioxolane equals 0.25:1 according to volume ratio to be mixed, and keeps gamma-butyrolacton with respect 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 made AA type battery of lithium-iron disulphide to make the electrolyte that conductivity is 7.5mS/cm with this electrolyte, and sample is designated as A13.
Embodiment 14
Method is identical with embodiment 1, and it is anhydrous 1 that different is, 2-dimethoxy-ethane and anhydrous 1; The 3-dioxolane equals 1.5:1 according to volume ratio to be mixed, and keeps gamma-butyrolacton with respect 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 made AA type battery of lithium-iron disulphide to make the electrolyte that conductivity is 7.5mS/cm with this electrolyte, and sample is designated as A14.
Embodiment 15
Method is identical with embodiment 1, and it is anhydrous 1 that different is, 2-dimethoxy-ethane and anhydrous 1; The 3-dioxolane equals 2.0:1 according to volume ratio to be mixed, and keeps gamma-butyrolacton with respect 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 made AA type battery of lithium-iron disulphide to make the electrolyte that conductivity is 7.5mS/cm with this electrolyte, and sample is designated as A15.
Embodiment 16
Method is identical with embodiment 1, and it is anhydrous 1 that different is, 2-dimethoxy-ethane and anhydrous 1; The 3-dioxolane equals 2.5:1 according to volume ratio to be mixed, and keeps gamma-butyrolacton with respect 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 made AA type battery of lithium-iron disulphide to make the electrolyte that conductivity is 7.5mS/cm with this electrolyte, and sample is designated as A16.
Comparative example 1
Method is identical with embodiment 1, and different is to adjust the addition of anhydrous lithium iodide to make the electrolyte that conductivity is 5.5mS/cm, makes AA type battery of lithium-iron disulphide with this electrolyte, and sample is designated as B1.
Comparative example 2
Method is identical with embodiment 1, and different is to adjust the addition of anhydrous lithium iodide to make the electrolyte that conductivity is 8.5mS/cm, makes AA type battery of lithium-iron disulphide with this electrolyte, and sample is designated as B2.
Comparative example 3
Method is identical with embodiment 1, and different is not contain gamma-butyrolacton in the electrolyte, and the addition of adjustment anhydrous lithium iodide is made AA type battery of lithium-iron disulphide to make the electrolyte that conductivity is 7.5mS/cm with this electrolyte, and sample is designated as B3.
Comparative example 4
Method is identical with embodiment 1; Different is to get 470ml anhydrous 1; 2-dimethoxy-ethane and 470ml are anhydrous 1, and 3-dioxolane mixed solvent (volume ratio 1:1) and gamma-butyrolacton 60ml mix in volume is the container of 2000ml, and the addition of adjustment anhydrous lithium iodide is 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 B4.
Comparative example 5
Method is identical with embodiment 1, and different is not contain gamma-butyrolacton in the electrolyte, and the addition of adjustment anhydrous lithium iodide is made AA type battery of lithium-iron disulphide to make the electrolyte that conductivity is 8.5mS/cm with this electrolyte, and sample is designated as B5.
Comparative example 6
Method is identical with embodiment 1; Different is, and to adopt thickness be that 20 microns the little porous septum of PP (polypropylene) is as the barrier film of battery; This barrier film is from U.S. Celgard company; Model is Celgard A765, is the synthetic polypropylene single-layer septum material of typical little porous, and closed pore temperature is about 170 ℃.Make AA type battery of lithium-iron disulphide with this barrier film, sample is designated as B6.
Comparative example 7
Method is identical with embodiment 1; Different is, and to adopt thickness be that PP (polypropylene)/PE (polyethylene)/three layers of little porous septum of PP (polypropylene) of 20 microns are as the barrier film of battery; This barrier film is from U.S. Celgard company; Be the synthetic three layers of diaphragm material of typical little porous, closed pore temperature is about 160 ℃.Make AA type battery of lithium-iron disulphide with this barrier film, sample is designated as B7.
Comparative example 8
Method is identical with embodiment 1, and different is to change the addition of anhydrous lithium iodide to make the electrolyte that conductivity is 6.0mS/cm, makes AA type battery of lithium-iron disulphide with this electrolyte, and sample is designated as B8.
The battery of the foregoing description and comparative example is carried out 50%DOD (describing referring to preceding text), and the battery number whether battery burns and burning takes place is observed in the experiment of puncturing then, and it is following that statistics is listed table 1 in:
The table 1 battery of lithium-iron disulphide 50%DOD experimental result that punctures
| Sample number | Electric Experimental cell sum/only punctures | The fuel cell number/only |
| A1 | 150 | 0 |
| A2 | 150 | 0 |
| A3 | 150 | 7 |
| A4 | 150 | 0 |
| A5 | 150 | 0 |
| A6 | 150 | 0 |
| A7 | 150 | 3 |
| A8 | 150 | 0 |
| A9 | 150 | 2 |
| A10 | 150 | 7 |
| A11 | 150 | 0 |
| A12 | 150 | 0 |
| A13 | 150 | 0 |
| A14 | 150 | 0 |
| A15 | 150 | 0 |
| A16 | 150 | 0 |
| B1 | 150 | 0 |
| B2 | 150 | 78 |
| B3 | 150 | 13 |
| B4 | 150 | 32 |
| B5 | 150 | 105 |
| B6 | 150 | 146 |
| B7 | 150 | 128 |
| B8 | 150 | 0 |
Can know that by last table when battery of the present invention being punctured when experiment, battery can not burn basically, even or burn, quantity is also controlled basically.When the battery to comparative example carried out same experiment, battery was easy to burn, and the burning probability is higher.
Above-mentioned battery is carried out discharge test, and every group of specimen number is 5, and method of testing adopts the digital camera accelerated test in the ansi standard; Be ANSI DCAM Acc; Be specially: apply the load discharge 2 seconds of 1500mW earlier, then the 650mW discharge is 28 seconds, repeats; Reach the cut-ff voltage of appointment up to battery, the umber of pulse of battery discharge is weighed battery performance when arriving 1.05V through cell voltage.The result adds up in table 2:
Table 2 battery of lithium-iron disulphide ANSI DCAM ACC discharge result/by the end of 1.05V
Can know that by last table the battery that embodiments of the invention obtained shows the performance no less than the comparative example battery in this discharge performance test.
The present invention is illustrated through the foregoing description, but should be understood that, the foregoing description just is used for for example and illustrative purposes, but not is intended to the present invention is limited in the described scope of embodiments.It will be appreciated by persons skilled in the art that in addition the present invention is not limited to the foregoing description, can also make more kinds of variants and modifications according to instruction of the present invention, these variants and modifications all drop in the present invention's scope required for protection.Protection scope of the present invention is defined by appended claims book and equivalent scope thereof.
Claims (14)
1. battery of lithium-iron disulphide, said battery comprises: the negative pole of being processed by lithium metal or its alloy, with positive pole and the organic electrolyte of ferrous disulfide as positive electrode active materials is provided with barrier film between said negative pole and the positive pole; It is characterized in that:
Said organic electrolyte has the conductivity of 6.5mS/cm to 8.0mS/cm;
Said organic electrolyte comprises organic solvent and is dissolved in lithium salts wherein; Said organic solvent is by gamma-butyrolacton, 1,2-dimethoxy-ethane and 1, and the 3-dioxolane is formed; Wherein, Gamma-butyrolacton is with respect to 1,2-dimethoxy-ethane and 1, and the volume feed of 3-dioxolane total amount is (0-5]: [95-100);
Said barrier film is the little porous septum of polyethylene.
2. according to claim 1, said organic electrolyte has the conductivity of 6.5mS/cm to 7.5mS/cm.
3. battery of lithium-iron disulphide according to claim 2, said organic electrolyte has the conductivity of 7.0mS/cm to 7.5mS/cm.
4. battery of lithium-iron disulphide according to claim 1, wherein, said volume feed is [0.5-5]: [95-99.5].
5. battery of lithium-iron disulphide according to claim 4, wherein, said volume feed is [1.5-3]: [97-98.5].
6. battery of lithium-iron disulphide according to claim 1, wherein, 1,2-dimethoxy-ethane and 1, the volume feed of 3-dioxolane is 0.25-2:1.
7. battery of lithium-iron disulphide according to claim 6, wherein, 1,2-dimethoxy-ethane and 1, the volume feed of 3-dioxolane is 0.5-1:1.
8. battery of lithium-iron disulphide according to claim 1, described lithium salts is for being selected from LiTFS, LiTFSI, LiI, LiBr, LiBF
4, LiClO
4And LiPF
6In one or more.
9. battery of lithium-iron disulphide according to claim 1, described lithium salts comprise the above LiI of 90 moles of %.
10. battery of lithium-iron disulphide according to claim 1, said lithium salts are LiI.
11. battery of lithium-iron disulphide according to claim 1, the thickness of said barrier film are 15 microns to 30 microns.
12. battery of lithium-iron disulphide according to claim 1, the thickness of said barrier film are 17 microns to 25 microns.
13. battery of lithium-iron disulphide according to claim 1, the thickness of said barrier film are 20 microns to 23 microns.
14. battery of lithium-iron disulphide according to claim 1, said barrier film are that closed pore temperature is smaller or equal to the little porous septum of 150 ℃ polyethylene.
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| CN107017442A (en) * | 2017-03-24 | 2017-08-04 | 李明 | Processing method in power battery recovery process |
| CN107565144A (en) * | 2016-06-30 | 2018-01-09 | 深圳新宙邦科技股份有限公司 | A kind of lithium pyrite battery |
| CN112002872A (en) * | 2020-09-07 | 2020-11-27 | 上海空间电源研究所 | Lithium-cobalt disulfide primary battery and preparation method thereof |
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| CN102270756A (en) * | 2010-09-25 | 2011-12-07 | 上海市凌桥环保设备厂有限公司 | Composite diaphragm for lithium ion battery |
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