CN100495804C - Lithium secondary battery - Google Patents
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- CN100495804C CN100495804C CNB2006800011743A CN200680001174A CN100495804C CN 100495804 C CN100495804 C CN 100495804C CN B2006800011743 A CNB2006800011743 A CN B2006800011743A CN 200680001174 A CN200680001174 A CN 200680001174A CN 100495804 C CN100495804 C CN 100495804C
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Abstract
A lithium secondary battery that is excellent in resistance to short-circuits and heat, is unlikely to suffer a capacity loss due to impact such as dropping, and has a high capacity. The lithium secondary battery includes: an electrode assembly including a strip-like positive electrode and a strip-like negative electrode that are wound together with a porous heat-resistant layer interposed therebetween; a non-aqueous electrolyte; and a battery can. The battery has a restricting part for restricting vertical movement of the electrode assembly. The distance A from the restricting part to the inner bottom face of the battery can and the width B of the negative electrode satisfy the relation: 0.965<=B/A<=0.995.
Description
Technical field
The present invention relates to a kind of have outstanding Short Circuit withstand and the higher lithium secondary battery of stable on heating fail safe.The present invention be more particularly directed to a kind ofly be used to prevent that battery is because of impacting as fall to producing the technology of capacitance loss.
Background technology
Lithium secondary battery receives publicity as the high-capacity power supply of mancarried device and other devices.In addition, lithium secondary battery also receives publicity recently day by day as the high output power of motor vehicle etc.Chemical cell such as lithium secondary battery have usually can make barrier film anodal and negative electricity insulation and maintenance electrolyte.In lithium secondary battery, the microporous barrier of mainly using polyolefin (as polyethylene, polypropylene etc.) to make is made barrier film.By the barrier film between positive pole and negative pole and insertion two electrodes is intertwined, the electrode assemblie of lithium secondary battery can manufacture the cylindrical of columniform or basic ellipse.
Columniform lithium secondary battery can be used as, for example, and the power supply of power tool and notebook computer.Columniform lithium secondary battery seals on can being crimped onto sealing plate by the opening edge with its battery case.For making sealing plate be fixed on the open-topped periphery of battery case, the slot part (narrow) that battery case has an internal diameter to reduce at the first half of its sidewall.Patent documentation 1 has proposed a kind of high power capacity design, satisfies relational expression: B/A=0.957 width B of negative pole (38mm) and the distance A from narrow to the battery case outer bottom (39.7mm) in this design.
Prismatic lithium secondary battery can be used as, for example, and the power supply of portable phone and digital still camera.Because prismatic lithium secondary battery is gone in the device than columniform easier peace, so they are just becoming universal day by day.In prismatic lithium secondary battery, connection electrode contacts with battery case easily with the lead-in wire of terminal, and this is different from columniform lithium secondary battery.When touching battery case, the polarity lead-in wire opposite with battery case can be short-circuited.Therefore usually insulator (below deserve to be called portion's insulator) is being set between the first half of electrode assemblie and the lid of battery case (insulation board).For further improving Short Circuit withstand, people also propose to be provided with insulator (to call lower isolator in the following text) (patent documentation 2) between the bottom of the Lower Half of electrode assemblie and battery case.
The electrode assemblie of prismatic lithium secondary battery manufactures usually the width B of distance A from the lower surface of top insulator to the battery case inner bottom surface and negative pole and satisfies relational expression: B/A≤0.96.The ratio of B/A is high more, and battery capacity is high more.Yet if the ratio of B/A is too high, electrode assemblie can be to twisting sensitivity, thereby cause directly contacting i.e. short circuit between positive pole and negative pole.In patent documentation 2, by the lower isolator as buffer is set, the ratio of B/A is set at up to 0.97.
Simultaneously, when lithium secondary battery under the thermal extremes environment during long-time preservation, its barrier film of being made by microporous barrier has tendencies toward shrinkage.If barrier film shrinks, the generation internal short-circuit thereby in fact so anodal and negative pole can contact with each other.Consider that recent development trend is to make the barrier film attenuation increase the capacity of lithium secondary battery simultaneously, prevent from therefore that internal short-circuit from becoming to be even more important.In case internal short-circuit takes place, the short circuit meeting enlarges because of the Joule heat that short circuit current produces, thereby causes battery overheated.
Therefore, when internal short-circuit takes place, enlarge, propose on electrode active material layers, to form the porous heat-resistant layer that contains inorganic filler (solid fine particle) and adhesive for suppressing this class short circuit.Aluminium oxide, silicon dioxide etc. can be used as inorganic filler.Inorganic filler is filled out in porous heat-resistant layer, the adhesive (patent documentation 3) bonded to one another of relatively small amount of filler grain herein.Because even porous heat-resistant layer at high temperature all has anti-contracility,, it under internal short-circuit, suppresses the overheated effect of battery so playing.
Patent documentation 1: the flat 11-354084 of Japanese patent application No..
Patent documentation 2: Japanese patent application No.2004-31263.
Patent documentation 3: the flat 7-220759 of Japanese patent application No..
Summary of the invention
The problem to be solved in the present invention
In order to realize having the lithium secondary battery of high power capacity and outstanding Short Circuit withstand, the proposal of patent documentation 1 or patent documentation 2 and the proposal combination of patent documentation 3 can be adopted.This combination has obviously reduced internal short-circuit, but when battery is subjected to impacting, during as the whereabouts, can cause tangible capacitance loss.
Consider the problems referred to above, one of purpose of the present invention provides a kind of lithium secondary battery that has outstanding Short Circuit withstand, can prevent the capacitance loss that falls to causing and can carry out the high power capacity design.
The method of dealing with problems
The present invention relates to a kind of lithium secondary battery, it comprises: have bottom, sidewall and open-topped battery case; Electrode assemblie; Nonaqueous electrolytic solution; And covering is in order to the open-topped sealing plate of the battery case of hold electrodes assembly and electrolyte.Electrode assemblie comprises and is inserted in the anodal and bar shaped negative pole of bar shaped that the porous heat-resistant layer between positive pole and the negative pole is intertwined.Positive pole comprises anodal core components and the anode active material layer that is coated on this core components, and negative pole comprises negative pole core components and the anode active material layer that is coated on this core components.Battery has the restriction site of restriction electrode assemblie vertical moving, and satisfies relational expression: 0.965≤B/A≤0.995 width B of distance A from this restriction site to the battery case bottom interior surface and negative pole.
The inner surface of battery case bottom has slight sunk part and ledge.Yet in the case, the difference in height between sunk part and ledge is no more than 0.05mm usually, therefore can ignore.In addition, the width B of negative pole is meant the length than minor face of bar shaped negative pole.That is to say that the width B of negative pole is corresponding to the maximum height place of electrode part in the cylindrical electrode assembly.
Lithium secondary battery according to the present invention has and comprises between porous heat-resistant layer and the positive pole or the barrier film of the microporous barrier between porous heat-resistant layer and the negative pole.
Porous heat-resistant layer is formed on, for example, and in anode active material layer and the anode active material layer on the surface of at least one.
Porous heat-resistant layer comprises, for example, and insulating packing and adhesive.Insulating packing with 100 weight portions is a benchmark, and the content of adhesive is preferably 1～10 weight portion.Porous heat-resistant layer preferably has 40～80% porosity.
Insulating packing preferably comprises inorganic oxide.Inorganic oxide preferably comprises at least a in aluminium oxide, silicon dioxide, magnesium oxide, titanium dioxide and the zirconia.
When electrode assemblie is cylindrical and battery case when being cylindrical substantially, restriction site preferably adopts the slot part of the battery case that the internal diameter that is arranged on the battery case sidewall first half reduces.During the change in depth of the slot part that reduces according to diameter when distance A, the distance of the inner surface bottom from the deepest part (the best part is protruded at the center towards battery case) of slot part to battery case is a distance A.
Lithium secondary battery according to the present invention has the insulator between electrode assemblie and sealing plate.In the case, when electrode assemblie when being prismatic for basic oval cylindrical and battery case, restriction site is preferably the Lower Half surface of insulator.In prismatic lithium secondary battery, from the restriction site to the battery case, preferably satisfy relational expression: 0.975≤B/A≤0.995 between the width B of the distance A of the inner surface of bottom and negative pole.
The invention effect
The present invention can provide a kind of and has outstanding Short Circuit withstand and thermal endurance, can avoid because of capacitance loss that impacts as fall to causing and the lithium secondary battery that higher capacity is provided.
Description of drawings
Fig. 1 is the generalized section of a cylindrical lithium secondary battery example of the present invention; And
Fig. 2 is the generalized section of a square lithium secondary battery example of the present invention.
Embodiment
The present invention relates to a kind of lithium secondary battery, it comprises: have bottom, sidewall and open-topped battery case; Electrode assemblie; Nonaqueous electrolytic solution; And covering is in order to the open-topped sealing plate of the battery case of hold electrodes assembly and electrolyte.This electrode assemblie comprises and is inserted in the anodal and bar shaped negative pole of bar shaped that the porous heat-resistant layer between positive pole and the negative pole is intertwined.Positive pole comprises anodal core components and the anode active material layer that is coated on this core components, and negative pole comprises negative pole core components and the anode active material layer that is coated on this core components.Battery has the restriction site of restriction electrode assemblie vertical moving, and satisfies relational expression: 0.965≤B/A≤0.995 between the width B of the distance A of the inner surface bottom from the restriction site to the battery case and negative pole.
The inventor has studied the electrode assemblie with porous heat-resistant layer by persistence and following two discoveries has been arranged.
At first, the electrode assemblie that has a porous heat-resistant layer is compared with the traditional electrode assembly that does not have porous heat-resistant layer and have less deformation in charge/discharge process.This may be that electrode and barrier film can not slide or move as a result because porous heat-resistant layer has than positive pole, negative pole and the lower surface smoothness of barrier film.
The second, when electrode assemblie suitable deformation did not take place, this electrode assemblie can not firmly be fixed in the battery case.Therefore, when this battery fell, the electrode in its electrode assemblie can move, thereby causes capacitance loss.
Based on these discoveries, in the present invention, the width B of negative pole and from the restriction site to the battery case ratio (ratio of B/A) of distance A of the inner surface of bottom be set as the scope higher than conventional value.When the ratio of B/A satisfies relational expression: during 0.965≤B/A≤0.995, move (especially when battery falls) of electrode obviously is suppressed in the electrode assemblie, thereby capacitance loss can not take place.
If the ratio of B/A surpasses 0.96, it is big that the distortion of electrode assemblie becomes, and this can cause short circuit usually.In addition, the negative pole width of lithium secondary battery is usually designed to the width greater than positive pole, so the deformation of negative pole problem especially.Yet, because the electrode assemblie among the present invention has porous heat-resistant layer, even near the edge of negative pole slight deformation close electrode assemblie upper surface or lower surface can not be short-circuited yet.Therefore, the ratio of B/A can be set at 0.965 or higher.According to the present invention, approach from the restriction site to the battery case distance A of the inner surface of bottom by the width that makes negative pole, can when improving anti-drop impact down, realize high power capacity.
If the ratio of B/A less than 0.965, then is difficult to realize high power capacity, in addition, battery has moved capacitance loss because of the electrode in the electrode assemblie probably when falling.On the other hand, if the ratio of B/A surpasses 0.995, negative pole is having obvious distortion near electrode assemblie upper surface or lower surface place.So porous heat-resistant layer is damaged, thereby make internal short-circuit be easy to take place.
When 0.965≤B/A≤0.995, can obtain that internal short-circuit can not take place, have high power capacity and the outstanding anti-lithium secondary battery of drop impact down.
Can have or not have the barrier film that comprises microporous barrier according to lithium secondary battery of the present invention.Barrier film is between porous heat-resistant layer and the positive pole or between porous heat-resistant layer and the negative pole.The effect of barrier film is porous heat-resistant layer frangible on the supporting construction.Therefore, for further improving anti-drop impact down, battery preferably has barrier film.
Microporous membrane material is preferably polyolefin, and this polyolefin is preferably polyethylene, polypropylene etc.Also can use and comprise polyethylene and polyacrylic microporous barrier simultaneously.Preferred 8～20 μ m of the thickness of microporous barrier play the effect of supporting porous heat-resistant layer and keeping the high power capacity design to guarantee it.
Porous heat-resistant layer can only be formed on the surface of anode active material layer or on the surface of anode active material layer.Perhaps, porous heat-resistant layer can be formed on the surface of the surface of anode active material layer and anode active material layer simultaneously.Yet in order to avoid internal short-circuit with reliable fashion, porous heat-resistant layer is preferably formed in and is designed to have on the surface of more large-area anode active material layer than anode active material layer.In addition, this porous heat-resistant layer can be formed on the active material layer on the side of core components or be formed on the active material layer on two sides of core components.In addition, porous heat-resistant layer preferably sticks on the surface of active material layer.
Porous heat-resistant layer can be thin slice independently.Yet, because lamelliform porous heat-resistant layer does not have high mechanical strength, so may be difficult to handle.In addition, porous heat-resistant layer can stick on the surface of barrier film.Yet, owing to barrier film at high temperature can shrink, so must keep a close eye on creating conditions of porous heat-resistant layer.For eliminating this class problem, porous heat-resistant layer also is preferably formed on the surface of anode active material layer or on the surface of anode active material layer.
Porous heat-resistant layer preferably comprises insulating packing and adhesive.Use scraping blade or die coater, the raw material slurry that will contain insulating packing and a little binder is coated on the surface of electrode active material layers or barrier film and after the drying, forms this porous heat-resistant layer.Use as a double-arm kneader, insulating packing, adhesive and liquid components are mixed, prepare the raw material slurry.
In addition, porous heat-resistant layer can be the fibroplastic film by the resin of high-fire resistance.The resin of high-fire resistance is preferably aromatic polyamides, polyamidoimide etc.Yet the porous heat-resistant layer that comprises insulating packing and adhesive has the structural strength higher than the fibroplastic film of high-fire resistance resin because of the effect of adhesive, so it is preferred.
The thickness of porous heat-resistant layer is preferably 0.5～20 μ m, and 1～10 μ m more preferably.If the thickness of porous heat-resistant layer is lower than 0.5 μ m, its effect that suppresses internal short-circuit reduces.In addition, if the thickness of porous heat-resistant layer surpasses 20 μ m, distance is excessive between positive pole and negative pole, and this can cause the output characteristic of battery to descend.
Insulating packing can comprise the resin bead of fiber or high-fire resistance, but preferably comprises inorganic oxide.Because inorganic oxide is hard, so even they can make the distance between positive pole and negative pole cause that at charge/discharge electrode still remains in the suitable scope when expanding.In inorganic oxide, especially preference such as aluminium oxide, silicon dioxide, magnesium oxide, titanium dioxide and zirconia, this is because they have higher electrochemical stability in the operational environment of lithium secondary battery.They can be individually or two or more be used in combination.
In the porous heat-resistant layer that comprises insulating packing and adhesive, insulating packing with 100 weight portions is a benchmark, the content of adhesive is preferably 1～10 weight portion, and 2～8 weight portions more preferably, to keep the mechanical strength and the ionic conductivity thereof of porous heat-resistant layer.Swelling inherently can take place because of the electrolyte that contains nonaqueous solvents in most adhesive and thickener.Therefore, if the content of adhesive surpasses 10 weight portions, adhesive can excessive swelling make the micropore closure of porous heat-resistant layer, thereby ionic conductivity is reduced and the generation of prevention cell reaction.On the other hand, if the content of adhesive is lower than 1 weight portion, the mechanical strength of porous heat-resistant layer reduces.
The adhesive that is used for porous heat-resistant layer is not particularly limited, but is preferably for example polyvinylidene fluoride (to call PVDF in the following text), polytetrafluoroethylene (to call PTFE in the following text) and polypropylene acid type rubber particles (for example BM-500B of Zeon company (trade name)).Preferably PTFE or BM-500B and thickener are used in combination.Thickener is not particularly limited, but is preferably for example carboxymethyl cellulose (to call CMC in the following text), poly(ethylene oxide) (to call PEO in the following text) and modified butadiene acrylonitrile rubber (for example BM-720H of Zeon company (trade name)).
The porosity that comprises the porous heat-resistant layer of insulating packing and adhesive is preferably 40%～80%, and more preferably 45%～65%, with the mechanical strength that keeps porous heat-resistant layer and improve its anti-drop impact down.Because porous heat-resistant layer has than positive pole, negative pole and the lower surface smoothness of barrier film, so the slip of electrode and barrier film (moving) is subjected to very big inhibition.So electrode assemblie is easy to move.Yet when the porous heat-resistant layer with 40%～80% porosity immersed an amount of electrolyte, electrode assemblie can swell to suitable degree.So the electrode assemblie of swelling has been pushed down the madial wall of battery case.When the effect that produces when 40%～80% porosity and the effect of B/A optimum ratio promoted mutually, anti-drop impact down was further enhanced.If porosity is lower than 40%, electrolyte does not fully soak into porous heat-resistant layer, so electrode assemblie does not swell to suitable degree.On the other hand, if porosity surpasses 80%, the mechanical strength of porous heat-resistant layer reduces.
Should be noted that the porosity of porous heat-resistant layer can be controlled by the median particle diameter, the content of adhesive and the drying condition of raw material slurry that change insulating packing.For example, rising baking temperature or increase desiccant hot air flowrate and can cause porosity to increase relatively.Porosity can be obtained by following calculation of parameter, for example, and the actual specific gravity of the content of the thickness of porous heat-resistant layer, insulating packing and adhesive and insulating packing and adhesive.The thickness of porous heat-resistant layer can be by taking electrode the SEM photo of several cross sections (for example 10 cross sections) and the average thickness of these several cross sections determine.In addition, porosity can be determined with mercury porosimeter.
Cylindrical lithium secondary battery has the electrode assemblie that the cross section is cylindrical (cylindrical) of circle substantially.In addition, cylindrical lithium secondary battery has cylindrical battery shell 100 as shown in Figure 1.This cylindrical battery shell one end opening and the other end seal with flat 110.With regard to common cylindrical lithium secondary battery, thereby the opening edge of battery case is crimped onto on the circumference of sealing plate 120 and seals its open top.In the case, the restriction site of restriction electrode assemblie vertical moving is arranged on the slot part 130 of the battery case 100 that having of the battery case 100 sidewall first halves reduce internal diameter.Slot part 130 also has the function of fixing seal plate 120.
Prismatic lithium secondary battery has the electrode assemblie of cross section for cylindrical (near oval-shaped cylindrical) of basic ellipse.In addition, square lithium secondary battery has the battery case 200 of as shown in Figure 2 prismatic (substantially for rectangle).This prismatic battery shell one end opening and the other end seal with flat 210.With regard to common square lithium secondary battery, the open top of battery case is by welding together sealing with its opening edge and metallic seal plate 220.In addition, insulator 230 (top insulator) between sealing plate 220 and electrode assemblie to prevent that the lead-in wire in the electrode from contacting with battery case 200.Insulator 230 has the contact conductor through hole, thereby insulator is moved hardly.Therefore, the restriction site of restriction electrode assemblie vertical moving is the lower surface of insulator 230.
The thickness of insulator is preferably 2%～10% of battery case height, thereby guarantees its function and reduce the dead angle.
In cylindrical lithium secondary battery, the vertical section that is used as the slot part of restriction site is subjected to the restriction of the mode of production to be generally V-arrangement or U-shaped.Therefore, the variation of distance A depends on the degree of depth as the slot part of restriction site.In the case, the distance of the inner surface of bottom is a distance A from the slot part deepest part to battery case.In the case, if the ratio of B/A be 0.965 or more than, can obtain enough anti-drop impacts down.Yet, consider the balance of high power capacity and anti-down drop impact, 0.970≤B/A≤0.990 more preferably in the cylindrical lithium secondary battery.
On the other hand, in square lithium secondary battery, the lower surface that is used as the insulator 230 of restriction site is flat.Therefore, for obtaining outstanding anti-drop impact down, the ratio of B/A preferred 0.975 or more than.In addition, consider the balance of high power capacity and anti-down drop impact, 0.975≤B/A≤0990 more preferably in the square lithium secondary battery.
Positive pole comprises anodal core components and the anode active material layer that is coated on each side of this core components.Anodal core components is the bar shaped that is suitable for twining and contains Al, Al alloy etc.Anode active material layer comprises as the positive electrode active materials of solvent and the optional components that optionally can comprise such as conductive agent and adhesive.These materials are not particularly limited, but preferred positive electrode active materials is the transition metal oxide that contains lithium.In containing the transition metal oxide of lithium, be preferably for example cobalt acid lithium, modification cobalt acid lithium, lithium nickelate, modification lithium nickelate, LiMn2O4 and modification LiMn2O4.
Negative pole comprises negative pole core components and the anode active material layer that is coated on each side of this core components.The negative pole core components is the bar shaped that is suitable for twining and contains Cu, Cu alloy etc.The width B of negative pole equals the width of negative pole core components.Anode active material layer comprises as the negative active core-shell material of solvent and optional components such as the conductive agent and the adhesive that optionally can comprise.These materials are not particularly limited, but preferred negative active core-shell material comprises various native graphites, various Delanium, siliceous composite material such as silicide, lithium metal and various alloy material.
The adhesive that is used for negative or positive electrode that exemplifies comprises PTFE, PVDF and butadiene-styrene rubber.The conductive agent that exemplifies comprises acetylene black, Ketjen black (registered trade mark) and various graphite.
Nonaqueous electrolytic solution preferably contains nonaqueous solvents and is dissolved in wherein lithium salts.Lithium salts is not particularly limited, but is preferably for example LiPF6 and LiBF4.These lithium salts can use separately, also can two or more be used in combination.Nonaqueous solvents is not particularly limited, but preferred example comprises ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC).These nonaqueous solventss can use separately, also can two or more be used in combination.
The material of battery case must be in the operating voltage range of lithium secondary battery electrochemical stability.For example, preferably use iron or aluminium.In addition, battery case can be electroplated with nickel or tin.
Fig. 1 is the generalized section of the cylindrical lithium secondary battery of the present invention of demonstration usefulness.
By with anodal 101 and negative pole 102 and barrier film 103 and be inserted in positive pole and negative pole between the porous heat-resistant layer (not shown) be intertwined, produce the cylindrical electrode assembly.Barrier film 103 is between porous heat-resistant layer and anodal 101.Yet if porous heat-resistant layer has enough thickness, barrier film 103 is unwanted.Electrode assemblie is inserted in the cylindrical battery shell 100.The first half of battery case 100 sidewalls has an internal diameter relatively less than the slot part 130 of other parts.Slot part 130 is put into battery case 100 backs at electrode assemblie and is formed.The vertical section of slot part 130 is U-shapeds.Afterwards, inject the electrolyte in the battery case 100.The open top of battery case 100 is by sealing sealing plate 120 being installed on the slot part 130 and the opening edge of battery case 100 being crimped onto on the circumference of sealing plate 120.
The negligible top of thickness non-conductive plate 106 and lower isolator plate 107 be arranged on electrode assemblie the top and under.One end of positive wire 104 is connected to anodal 101 core components, and the other end is connected to the inside that is arranged on sealing plate 120 lower surfaces and does not hold 108a.It is continuous that inside is not held between 108a and outside anodal terminal 108.One end of cathode conductor (not shown) is connected to the core components of negative pole 102, and the other end is connected to the inner bottom surface of battery case 100.
Fig. 2 is the generalized section of the square lithium secondary battery of the present invention of demonstration usefulness.
By with positive pole and negative pole and barrier film and be inserted in positive pole and negative pole between porous heat-resistant layer be intertwined, produce nearly oval-shaped cylindrical electrode assembly.Electrode assemblie 201 is inserted into basic in (prismatic) battery case 200 of rectangle.After electrode assemblie 201 was put into battery case 200, the top that insulator 230 is installed in electrode assemblie 201 was with the end that prevents battery case 200 or positive wire 202 and the short circuit between the cathode conductor 203.Insulator 230 is fixed near the opening of battery case 200.
Sealing plate 220 has the negative pole end 207 that the periphery is furnished with insulation spacer 206.Cathode conductor 203 is connected to negative pole end 207, and positive wire 202 is connected to the lower surface of sealing plate 220.
The hand-hole of electrolyte from sealing plate 220 is injected in the battery case 200, and this hand-hole seals with sealing plug 209 by welding.The open top of battery case 200 seals by fitting tight plate 220 and with laser welding opening edge and sealing plate 220.
To specify content of the present invention for example below.
Embodiment 1
In this embodiment, explanation is cylindrical lithium secondary battery shown in Figure 1.
(battery 1)
(i) Zheng Ji preparation
Use a double arm kneading mixer, the PVDF#1320 of the Kureha chemical industry Co., Ltd of the cobalt of 3kg acid lithium, 1kg (N-N-methyl-2-2-pyrrolidone N-(below the be called NMP) solution that contains 12wt%PVDF), the acetylene black of 90g and an amount of NMP are stirred, prepare the cathode mix slurry.The slurry of gained is coated on two sides of the anodal core components that comprises 15 μ m thick aluminum foils, has formed the positive pole that has anode active material layer after drying and the roll-in.This anodal gross thickness is 160 μ m.This positive pole is cut into the band that width is 56.5mm.
The (ii) preparation of negative pole
Use a double-arm kneader, BM-400B (aqueous dispersion that contains the 40wt% modified styrene butadiene rubber), the CMC of 30g of the Zeon company of the Delanium of 3kg, 75g and an amount of water are stirred, prepare the negative pole mixture paste.The slurry of gained is coated on two sides of the negative pole core components that comprises the thick Copper Foil of 10 μ m, has formed the negative pole that has anode active material layer after drying and the roll-in.The gross thickness of this negative pole is 180 μ m.This negative pole is cut into the band that width is 57.5mm.
The (iii) formation of porous heat-resistant layer
Use a double-arm kneader, the BM-720H (nmp solution (adhesive) that contains 8wt% modified polypropene nitrile rubber) and an amount of NMP of Zeon company that with the median particle diameter of 970g is aluminium oxide (insulating packing), the 375g of 0.3 μ m stirs, and prepares the raw material slurry.The raw material slurry of gained is coated on the surface of anode active material layer, and with 130 ℃ hot-air (flow: 1.5m/min) dry 4 minutes, thereby form the thick porous heat-resistant layer of 5 μ m.The porosity of each porous heat-resistant layer is 50%.Porosity is according to following calculation of parameter: the thickness of the porous heat-resistant layer of determining by the SEM photo of taking its cross section; The content of aluminium oxide in the porous heat-resistant layer of the given area that obtains by x-ray fluorescence analysis; The actual specific gravity of aluminium oxide and adhesive; And the weight ratio between aluminium oxide and adhesive.
The (iv) preparation of electrolyte
LiPF6 is dissolved in the solvent mixture of the ethylene carbonate that volume ratio is 1:1:1 (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) with the concentration of 1mol/liter, and the ethylene carbonate of this solution and 3wt% is mixed, prepare electrolyte.
(the v) manufacturing of battery
By (available from Celgard K.K., width: barrier film 60.7mm) is intertwined, and produces the cylindrical electrode assembly with forming the negative pole of porous heat-resistant layer and the anodal polyethene microporous membrane thick with inserting therebetween 10 μ m on two sides.
Then this electrode assemblie is inserted into (internal diameter: 18mm) in the cylindrical battery shell of iron of nickel plating.Should be noted that top non-conductive plate and lower isolator plate lay respectively at electrode assemblie the top and under because they are extremely thin, so its thickness can be ignored.Thereafter, at the first half of battery case sidewall one slot part is set, the internal diameter of battery case reduces herein.The vertical section of this slot part is a U-shaped, and the degree of depth of the slot part that reduces of this diameter is 1.5 μ m.Distance A from the inner bottom surface of battery case to the deepest part of this slot part is 60.5mm.
Then the electrolyte of 5.5g is injected into the hollow bulb of electrode assemblie, thereby makes electrode assemblie immerse electrolyte., sealing plate is installed on the slot part of battery case thereafter, and with the opening edge of battery case be crimped onto sealing plate on the circumference.The internal diameter of the cylindrical lithium secondary battery that produces is 18mm, highly is 65.0mm, and design capacity is 2200mAh.The ratio of B/A (ratio of width B of negative pole (57.5mm) and distance A (60.5mm)) is 0.950.
(battery 2～5)
Make cylindrical lithium secondary battery 2～5 with the manufacture method identical with battery 1, different just negative pole width B become 58.5mm, 59.2mm, 60.2mm and 61.2mm respectively, anodal width becomes 57.5mm, 58.2mm, 59.2mm and 60.2mm respectively, and design capacity becomes 2239mAh, 2266mAh, 2305mAh and 2244mAh respectively.The ratio of B/A is 0.967 (battery 2), 0.979 (battery 3), 0.995 (battery 4) and 1.012 (batteries 5) in the various batteries.
(battery 6)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 3, different just porous heat-resistant layer be formed on the surface of anode active material layer and not on the surface of anode active material layer.
(battery 7)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 4, different just porous heat-resistant layer be formed on the surface of anode active material layer and not on the surface of anode active material layer.
(battery 8)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 3, the different just thickness of porous heat-resistant layer become 15 μ m and barrier film of no use is made electrode assemblie.
(battery 9)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 3, the aluminium oxide in the different just porous heat-resistant layer become magnesium oxide with same median particle diameter.
(battery 10)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 3, the aluminium oxide in the different just porous heat-resistant layer become silicon dioxide with same median particle diameter.
(battery 11)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 3, the aluminium oxide in the different just porous heat-resistant layer become titanium dioxide with same median particle diameter.
(battery 12)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 3, the aluminium oxide in the different just porous heat-resistant layer become zirconia with same median particle diameter.
(battery 13)
The forming process of porous heat-resistant layer is as follows.
The anhydrous calcium chloride of 65g drying is added among the NMP of 1kg, and in reactor, mixture is heated to 80 ℃ it is dissolved fully.The nmp solution of the calcium chloride of gained is cooled to room temperature, and then the p-phenylenediamine (PPD) with 32g adds wherein and dissolving fully., reactor placed 20 ℃ thermostatic chamber, and in 1 hour, progressively the dichloroterephthalicacid acid of 58g is joined in the nmp solution thereafter.This nmp solution was placed 1 hour so that polymerization reaction is carried out in 20 ℃ of thermostatic chambers, thus synthetic PPTA (to call PPTA in the following text).
After reaction is finished, nmp solution (polymer fluid) is relayed vacuum chamber and decompression is stirred 30 minutes with degasification from thermostatic chamber.With the polymer fluid of the nmp solution of calcium chloride dilution gained, prepare the nmp solution of the aromatic polyamide resin that contains 1.4wt%PPTA.
With scraping blade the nmp solution of the aromatic polyamide resin of gained is coated on the surface of barrier film and with 80 ℃ hot-air (flow: 0.5m/sec) drying.Fully clean the aromatic polyamide resin film of gained with pure water, to remove calcium chloride and in film, to form little pore.Then with this film drying, thereby on a surface of barrier film, form the thick porous heat-resistant layer of 5 μ m.The porosity of this porous heat-resistant layer is 48%.Electrode assemblie manufactures porous heat-resistant layer is contacted with positive pole.Porous heat-resistant layer is not formed on the anode active material layer.Except that above-mentioned difference, use the manufacture method identical to make cylindrical lithium secondary battery with battery 3.
(battery 14)
The forming process of porous heat-resistant layer is as follows.
Monochloro-benzene three acid anhydrides of 21g and the diaminodiphenyl ether of 20g are joined among the NMP of 1kg, and they are at room temperature mixed, prepare nmp solution (the polyamic acid content: 3.9wt%) of polyamic acid.Be coated on the surface of barrier film with the polyamic acid nmp solution of scraping blade gained.With the coated film of gained hot-air drying (flow:, thereby form polyamidoimide 0.5m/sec) so that polyamic acid is dehydrated into ring with 80 ℃.By this method, on a surface of barrier film, form the thick porous heat-resistant layer of 5 μ m.The porosity of this porous heat-resistant layer is 47%.Utmost point assembly manufactures porous heat-resistant layer is contacted with positive pole.Porous heat-resistant layer is not formed on the anode active material layer.Except that these differences, use the manufacture method identical to make cylindrical lithium secondary battery with battery 3.
(battery 15)
The nmp solution of the aromatic polyamide resin that will make with the method identical with battery 13 with scraping blade is coated on level and smooth stainless steel (SUS) plate, and filming 120 ℃, drying under reduced pressure 10 hours gained.Then this is filmed and from the SUS plate, separate, thereby obtain the porous heat-resistant layer of the thick individual sheets formula of 15 μ m.The porosity of this porous heat-resistant layer is 51%.By porous heat-resistant layer, but do not comprise barrier film, be intertwined, produce electrode assemblie positive pole and negative pole and insertion this sheet type therebetween.Porous heat-resistant layer is not formed on the anode active material layer.Except that above-mentioned difference, use the manufacture method identical to make cylindrical lithium secondary battery with battery 3.
(battery 16)
The nmp solution of the polyamic acid that will make with the method identical with battery 14 with scraping blade is coated on level and smooth stainless steel (SUS) plate.(flow: 0.5m/sec) drying is so that polyamic acid is dehydrated into ring with 80 ℃ hot-air with the coating of gained.To film then and from the SUS plate, separate, thereby obtain the porous heat-resistant layer of the thick individual sheets formula of 15 μ m.The porosity of this porous heat-resistant layer is 52%.By porous heat-resistant layer, but do not comprise barrier film, be intertwined, produce electrode assemblie positive pole and negative pole and insertion this sheet type therebetween.Porous heat-resistant layer is not formed on the anode active material layer.Except that above-mentioned difference, use the manufacture method identical to make cylindrical lithium secondary battery with battery 3.
(battery 17)
The forming process of porous heat-resistant layer is as follows.
Use a double-arm kneader, the BM-720H of the Zeon company of the aluminium oxide (median particle diameter is 0.3 μ m) of 995g, 62.5g and an amount of NMP are stirred, prepare the raw material slurry.The raw material slurry of gained is coated on the surface of anode active material layer, and with 130 ℃ hot-air (flow: 1.5m/min) dry 4 minutes, thereby form the thick porous heat-resistant layer of 5 μ m.The porosity of each porous heat-resistant layer is 61%.Except that these differences, use the manufacture method identical to make cylindrical lithium secondary battery with battery 3.
(battery 18)
The forming process of porous heat-resistant layer is as follows.
Use a double-arm kneader, the BM-720H of the Zeon company of the aluminium oxide (median particle diameter is 0.3 μ m) of 990g, 125g and an amount of NMP are stirred, prepare the raw material slurry.The raw material slurry of gained is coated on the surface of anode active material layer, and with 130 ℃ hot-air (flow: 1.5m/min) dry 4 minutes, thereby form the thick porous heat-resistant layer of 5 μ m.The porosity of each porous heat-resistant layer is 57%.Except that these differences, use the manufacture method identical to make cylindrical lithium secondary battery with battery 3.
(battery 19)
The forming process of porous heat-resistant layer is as follows.Use a double-arm kneader, the BM-720H of the Zeon company of the aluminium oxide (median particle diameter is 0.3 μ m) of 900g, 1250g and an amount of NMP are stirred, prepare the raw material slurry.The raw material slurry of gained is coated on the surface of anode active material layer, and with 130 ℃ hot-air (flow: 1.5m/mim) dry 4 minutes, thereby form the thick porous heat-resistant layer of 5 μ m.The porosity of each porous heat-resistant layer is 42%.Except that these differences, use the manufacture method identical to make cylindrical lithium secondary battery with battery 3.
(battery 20)
The forming process of porous heat-resistant layer is as follows.
Use a double-arm kneader, the BM-720H of the Zeon company of the aluminium oxide (median particle diameter is 0.3 μ m) of 800g, 2500g and an amount of NMP are stirred, prepare the raw material slurry.The raw material slurry of gained is coated on the surface of anode active material layer, and with 130 ℃ hot-air (flow: 1.5m/mim) dry 4 minutes, thereby form the thick porous heat-resistant layer of 5 μ m.The porosity of each porous heat-resistant layer is 35%.Except that these differences, use the manufacture method identical to make cylindrical lithium secondary battery with battery 3.
(battery 21～25)
Make cylindrical lithium secondary battery 21～25 with the manufacture method identical with battery 3, different just are used for dry coated raw material slurry and become 0.5m/min, 1m/min, 2m/min, 5m/min and 8m/min respectively with the flow of the hot-air that forms the porous heat-resistant layer process.The porosity of the porous heat-resistant layer of various batteries is 30% (battery 21), 42% (battery 22), 60% (battery 23), 78% (battery 24) and 89% (battery 25).
(battery 26)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 1, the different just thickness of barrier film become 15 μ m and do not have porous heat-resistant layer to form.
(battery 27)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 2, the different just thickness of barrier film become 15 μ m and do not have porous heat-resistant layer to form.
(battery 28)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 3, the different just thickness of barrier film become 15 μ m and do not have porous heat-resistant layer to form.
(battery 29)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 4, the different just thickness of barrier film become 15 μ m and do not have porous heat-resistant layer to form.
(battery 30)
Make cylindrical lithium secondary battery with the manufacture method identical with battery 5, the different just thickness of barrier film become 15 μ m and do not have porous heat-resistant layer to form.
Various batteries carry out twice precharge and discharge, and preservation 7 days under 45 ℃ of environment.Afterwards, they are carried out following assessment.Table 1, table 2 and table 3 have been summarized feature, battery design and the assessment result of porous heat-resistant layer respectively.
(internal short-circuit inspection)
Various batteries are all made 100 samples.These sample batteries discharge by following condition under 20 ℃ environment, and measure their open circuit voltage.These batteries under 45 ℃ environment preservation 10 day also once more measured their open circuit voltage thereafter.When battery open circuit voltage difference before and after the preservation under 45 ℃ of environment is 0.3V or when above, can determine that this class battery is in the internal short-circuit state.The incidence of internal short-circuit is as shown in table 3.
Constant current charge: charging current 1500mA/ end of charge voltage 4.2V;
Constant voltage charge: charging voltage 4.2V/ charging termination electric current 100mA.
(drop test)
The battery of process internal short-circuit inspection charges by following condition under 20 ℃ of environment and discharges, and obtains their discharge capacity.
Constant current charge: charging current 1500mA/ end of charge voltage 4.2V;
Constant voltage charge: charging voltage 4.2V/ charging termination electric current 100mA;
Constant-current discharge: discharging current 2200mA/ final discharging voltage 3V.
Thereafter, these batteries repeat 30 times from the 16cm eminence under 20 ℃ of environment, charge by above-mentioned condition then and discharge, and obtain their discharge capacity.So percentage of discharge capacity before the relative drop test of discharge capacity after the acquisition drop test.The result of anti-drop impact down is as shown in table 3.
(internal short-circuit inspection after the drop test)
After the drop test, use with drop test before identical method check internal short-circuit of battery.The result who falls behind the internal short-circuit incidence down is as shown in table 3.
(high output characteristic)
Various batteries charge by following condition under 20 ℃ of environment and discharge, and obtain their discharge capacity.
Constant current charge: charging current 1500mA/ end of charge voltage 4.2V;
Constant voltage charge: charging voltage 4.2V/ charging termination electric current 100mA;
Constant-current discharge: discharging current 440mA/ final discharging voltage 3V;
Constant current charge: charging current 1500mA/ end of charge voltage 4.2V;
Constant voltage charge: charging voltage 4.2V/ charging termination electric current 100mA;
Constant-current discharge: discharging current 4400mA/ final discharging voltage 3V.
So can obtain the discharge capacity of battery under the 4400mA percentage of its discharge capacity under 440mA relatively.The high output characteristic result is as shown in table 3.
(nail puncture test)
Various batteries charge to the cut-ff voltage of 4.35V under the charging current of 2200mA.Under 20 ℃ environment, iron nail (diameter is 2.7mm) is knocked in the speed of 5mm/sec in the sidewall of battery of various chargings, and with the thermocouple measurement battery temperature that invests on the battery sidewall.Battery temperature after 90 seconds is as shown in table 3.
Table 1
| Battery | Porous heat-resistant layer (μ m) | The position of porous heat-resistant layer | Barrier film (μ m) | Filler | Binder content (wt%) | Porosity (%) |
| 1 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 50 |
| 2 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 50 |
| 3 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 50 |
| 4 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 50 |
| 5 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 50 |
| 6 | 5 | Anodal | 10 | Aluminium oxide | 3 | 50 |
| 7 | 5 | Anodal | 10 | Aluminium oxide | 3 | 50 |
| 8 | 15 | Negative pole | Do not have | Aluminium oxide | 3 | 50 |
| 9 | 5 | Negative pole | 10 | Magnesium oxide | 3 | 50 |
| 10 | 5 | Negative pole | 10 | Silicon dioxide | 3 | 50 |
| 11 | 5 | Negative pole | 10 | Titanium dioxide | 3 | 50 |
| 12 | 5 | Negative pole | 10 | Zirconia | 3 | 50 |
| 13 | 5 | Barrier film | 10 | Aromatic polyamides | 48 | |
| 14 | 5 | Barrier film | 10 | Polyamidoimide | 47 | |
| 15 | 15 | Thin slice sheet independently | Do not have | Aromatic polyamides | 51 | |
| 16 | 15 | Thin slice sheet independently | Do not have | Polyamidoimide | 52 | |
| 17 | 5 | Negative pole | 10 | Aluminium oxide | 0.5 | 61 |
| 18 | 5 | Negative pole | 10 | Aluminium oxide | 1 | 57 |
| 19 | 5 | Negative pole | 10 | Aluminium oxide | 10 | 42 |
| 20 | 5 | Negative pole | 10 | Aluminium oxide | 20 | 35 |
| 21 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 30 |
| 22 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 42 |
| 23 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 60 |
| 24 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 78 |
| 25 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 89 |
| 26 | Do not have | 15 | ||||
| 27 | Do not have | 15 | ||||
| 28 | Do not have | 15 | ||||
| 29 | Do not have | 15 | ||||
| 30 | Do not have | 15 |
Table 2
| Battery | Negative pole width B (mm) | Anodal width (mm) | Design capacity (mAh) | B/A |
| 1 | 57.5 | 56.5 | 2200 | 0.950 |
| 2 | 58.5 | 57.5 | 2239 | 0.967 |
| 3 | 59.2 | 58.2 | 2266 | 0.979 |
| 4 | 60.2 | 59.2 | 2305 | 0.995 |
| 5 | 61.2 | 60.2 | 2344 | 1.012 |
| 6 | 59.2 | 58.2 | 2266 | 0.979 |
| 7 | 60.2 | 59.2 | 2305 | 0.995 |
| 8 | 59.2 | 58.2 | 2266 | 0.979 |
| 9 | 59.2 | 58.2 | 2266 | 0.979 |
| 10 | 59.2 | 58.2 | 2266 | 0.979 |
| 11 | 59.2 | 58.2 | 2266 | 0.979 |
| 12 | 59.2 | 58.2 | 2266 | 0.979 |
| 13 | 59.2 | 58.2 | 2266 | 0.979 |
| 14 | 59.2 | 58.2 | 2266 | 0.979 |
| 15 | 59.2 | 58.2 | 2266 | 0.979 |
| 16 | 59.2 | 58.2 | 2266 | 0.979 |
| 17 | 59.2 | 58.2 | 2266 | 0.979 |
| 18 | 59.2 | 58.2 | 2266 | 0.979 |
| 19 | 59.2 | 58.2 | 2266 | 0.979 |
| 20 | 59.2 | 58.2 | 2266 | 0.979 |
| 21 | 59.2 | 58.2 | 2266 | 0.979 |
| 22 | 59.2 | 58.2 | 2266 | 0.979 |
| 23 | 59.2 | 58.2 | 2266 | 0.979 |
| 24 | 59.2 | 58.2 | 2266 | 0.979 |
| 25 | 59.2 | 58.2 | 2266 | 0.979 |
| 26 | 57.5 | 56.5 | 2200 | 0.950 |
| 27 | 58.5 | 57.5 | 2239 | 0.967 |
| 28 | 59.2 | 58.2 | 2266 | 0.979 |
| 29 | 60.2 | 59.2 | 2305 | 0.995 |
| 30 | 61.2 | 60.2 | 2344 | 1.012 |
Table 3
| Battery | Short circuit incidence (%) | Anti-drop impact (%) down | Fall behind short circuit incidence (%) down | High output characteristic (%) | Nail thorn back battery temperature (℃) |
| 1 | 0 | 93.0 | 2 | 90.3 | 86 |
| 2 | 0 | 99.8 | 1 | 91.4 | 85 |
| 3 | 0 | 99.9 | 0 | 90.6 | 84 |
| 4 | 0 | 99.7 | 0 | 92.3 | 86 |
| 5 | 24 | 99.8 | 2 | 91.9 | 83 |
| 6 | 2 | 100.0 | 0 | 90.2 | 83 |
| 7 | 14 | 99.5 | 9 | 88.7 | 90 |
| 8 | 3 | 99.7 | 19 | 86.6 | 83 |
| 9 | 0 | 99.7 | 0 | 88.9 | 84 |
| 10 | 0 | 99.8 | 0 | 88.7 | 86 |
| 11 | 0 | 99.9 | 2 | 88.6 | 81 |
| 12 | 0 | 99.9 | 0 | 88.9 | 86 |
| 13 | 0 | 99.7 | 8 | 89.2 | 86 |
| 14 | 0 | 99.6 | 9 | 89.5 | 82 |
| 15 | 3 | 99.5 | 16 | 90.1. | 91 |
| 16 | 1 | 99.8 | 14 | 90.6 | 92 |
| 17 | 0 | 99.8 | 11 | 90.1 | 94 |
| 18 | 0 | 99.8 | 0 | 88.9 | 89 |
| 19 | 0 | 99.8 | 2 | 83.8 | 80 |
| 20 | 0 | 99.9 | 0 | 79.5 | 80 |
| 21 | 0 | 95.7 | 0 | 82.4 | 83 |
| 22 | 0 | 98.6 | 0 | 87.9 | 84 |
| 23 | 0 | 99.8 | 0 | 89.0 | 88 |
| 24 | 0 | 99.7 | 6 | 90.5 | 85 |
| 25 | 0 | 100.0 | 10 | 93.4 | 90 |
| 26 | 0 | 99.7 | 0 | 88.1 | 128 |
| 27 | 15 | 99.9 | 0 | 88.2 | 124 |
| 28 | 22 | 99.8 | 0 | 87.9 | 126 |
| 29 | 30 | 99.8 | 0 | 89.1 | 130 |
| 30 | 46 | 99.8 | 0 | 88.8 | 124 |
Relatively from slot part (restriction site) the battery 1 too small to the distance A of battery case inner bottom surface, capacity density is more less in the negative pole width B, and anti-in addition drop impact is lower down.After the drop test, battery 1 taken apart observe, found that the electrode that twines electrode assemblie has mobile.
Internal short-circuit does not take place because of the effect of porous heat-resistant layer in battery 1, but effective area (anodal and negative pole area respect to one another) reduce to cause its capacitance loss.Because of being furnished with porous heat-resistant layer, its electrode assemblie can resist deformation, so it can not firmly be fixed on the inboard of battery case.Therefore the electrode that twines electrode assemblie may be moved when repeating.
On the other hand, relatively from the slot part battery 5 excessive to the distance A of battery case inner bottom surface, anti-short-circuit is lower in the negative pole width B.The sample of determining to be in the battery 5 of internal short-circuit attitude taken apart observe.Found that the porous heat-resistant layer on the negative terminal surface has damage at the first half of electrode assemblie.Find that also barrier film ftractures.
In the battery 2～4 of ratio 0.965～0.995 of B/A, anti-short-circuit is higher, and anti-in addition drop impact down is improved.Battery of the present invention also is furnished with porous heat-resistant layer except that barrier film.Therefore, though when negative pole than anodal wide, when the electrode assemblie first half has slight deformation, the double-decker of being made up of porous heat-resistant layer and barrier film insulate crushed element.In addition, because the ratio of B/A is higher, electrode assemblie firmly is clipped between the inner bottom surface of slot part and battery case.Therefore the anti-drop impact down of battery may be improved.
In the battery 26～30 that does not have porous heat-resistant layer, the anti-influence of position, the unrestricted position of drop impact down all is good.It is believed that do not have the electrode assemblie of porous heat-resistant layer to be deformed to an appropriate level, so it firmly is fixed in the battery case.Even when these batteries fall, cause the electrode of the winding electrode assemblie of capacitance loss to move and therefore to be suppressed.Yet these batteries 26～30 are obviously overheated in nail puncture test.In addition, in identical with battery 2～4 respectively battery 27～29 in restriction site position, anti-short-circuit is lower.It is believed that the negative pole of these batteries 27～29 has slight deformation.Yet because these batteries do not have porous heat-resistant layer, when barrier film because of negative pole deformation cracking took place, internal short-circuit can not prevent.
In battery 6 and 7, porous heat-resistant layer is formed on the surface of anode active material layer.In these two kinds of batteries, the battery 7 with wideer negative pole demonstrates low relatively anti-short-circuit.This may be because porous heat-resistant layer is formed on the surface of the anode active material layer narrower than anode active material layer, so negative terminal surface contacts with the top edge of positive pole at the first half of electrode assemblie.
In the battery 8 that does not have barrier film, the anti-short-circuit after it falls is lower slightly.More frangible on its porous heat-resistant layer structure than barrier film.So, porous heat-resistant layer fallen percussion and local damage, thus be short-circuited.
Have in the battery 13 and 14 of the porous heat-resistant layer of being made by heat stable resin at membrane surface, the anti-short-circuit after falling is lower slightly.The mechanical strength of the porous heat-resistant layer that heat stable resin is made is lower than the mechanical strength of the porous heat-resistant layer that comprises insulating packing and adhesive.May therefore be short-circuited by the whereabouts percussion.
Have independently the porous heat-resistant layer thin slice and do not having in the battery 15 and 16 of barrier film, anti-short-circuit that their fall behind down is lower than the anti-short-circuit of battery 13 and 14 times backwardnesss of battery.This comes from this fact, and promptly the intensity of the porous heat-resistant layer intensity difference made of heat stable resin and porous heat-resistant layer is not improved because of lacking of barrier film.
Contain in porous heat-resistant layer in the battery 17 of 0.5wt% adhesive, the anti-short-circuit after falling is lower slightly.This may be because the adhesive of low content has weakened the adhesion of filler grain, thereby causes the mechanical strength of porous heat-resistant layer relatively poor.
On the other hand, in the battery 20 that contains the 20wt% adhesive, high output characteristic is lower.This may be because excessive adhesive has reduced the porosity of porous heat-resistant layer, and in addition, excessive adhesive is with the electrolyte swelling, thereby makes the micropore of porous heat-resistant layer closed and reduced ionic conductivity.On the other hand, be in the battery 18～19 of 1wt%～10wt% at binder content, anti-short-circuit and high output characteristic all are good.
In the battery 21 of the porous heat-resistant layer that has 30% porosity that obtains because of the control drying condition, anti-drop impact is lower slightly down.Its reason may be as follows.Because porosity is lower, porous heat-resistant layer is not soaked into electrolyte fully, so the swelling of electrode assemblie is less.Therefore, can not prevent that electrode assemblie from moving when falling.In the battery 25 of the porous heat-resistant layer with 89% porosity, the anti-short-circuit after falling is lower slightly.This may be because the mechanical strength of porous heat-resistant layer is relatively poor.
On the other hand, in having the battery 22～24 that porosity is 40%～80% porous heat-resistant layer, anti-drop impact down and fall after anti-short-circuit all be good.Its reason may be as follows.Because optimized porosity, the mechanical strength of porous heat-resistant layer is maintained.In addition, porous heat-resistant layer swells to an appropriate level with electrolyte.The result has prevented moving of electrode assemblie.
Embodiment 2
In this embodiment, explanation is square lithium secondary battery shown in Figure 2.
(battery 31)
Except that following difference, use the manufacture method identical to make electrode assemblie with embodiment 1.Anodal gross thickness becomes 150 μ m, and anodal width becomes 42.7mm.The gross thickness of negative pole becomes 150 μ m, and the width of negative pole becomes 43.7mm.The width of barrier film becomes 47mm.The shape of electrode assemblie becomes the cylindrical of ellipse.
The electrode assemblie of gained is inserted 49mm height (bottom thickness: 0.5mm), in the prismatic battery shell of 34mm is wide and 5.2mm is thick aluminium.After the insulator that 1.5mm is thick is installed in the electrode assemblie top, 2.5g and embodiment 1 identical electrolyte is injected in the battery case.Distance A from the inner bottom surface of battery case to the insulator lower surface is 46.0mm.The Lower Half that should be noted that electrode assemblie is by heat insulating lamella and battery case insulation, but because heat insulating lamella is extremely thin, its thickness can be ignored.
Thereafter, the rectangular seal plate that 1.0mm is thick is installed in the open top of battery case, and with laser with the opening edge of battery case and sealing plate peripheral solder be in the same place.The height of the square lithium secondary battery of making is 50mm, and width is 34mm, and thickness is 5.2mm, and design capacity is 950mAh.The ratio of B/A (ratio of negative pole width B (43.7mm) and distance A (46.0mm)) is 0.95.
(battery 32～35)
Make square lithium secondary battery 32～35 with the manufacture method identical with battery 31, different just negative pole width B become 44.6mm, 45mm, 45.7mm and 46.5mm respectively, anodal width becomes 43.6mm, 44mm, 44.7mm and 45.5mm respectively, and design capacity becomes 970mAh, 979mAh, 994mAh and 1012mAh respectively.The ratio of B/A is 0.970 (battery 32), 0.978 (battery 33), 0.993 (battery 34) and 1.011 (batteries 35) in the various batteries.
(battery 36 and 37)
Use the manufacture method identical to make square lithium secondary battery 36 and 37 respectively with battery 33 and 34, different just porous heat-resistant layer be formed on the surface of anode active material layer and not on the surface of anode active material layer.
(battery 38)
Make square lithium secondary battery with the manufacture method identical with battery 33, the different just thickness of porous heat-resistant layer become 15 μ m and barrier film of no use is made electrode assemblie.
(battery 39～42)
Make square lithium secondary battery 39～42 with the manufacture method identical with battery 33, the aluminium oxide in the different just porous heat-resistant layer become magnesium oxide, silicon dioxide, titanium dioxide and zirconia respectively with same median particle diameter.(battery 43～50)
Make square lithium secondary battery 43～50 with the manufacture method identical with battery 33, different just used the porous heat-resistant layer identical respectively with battery 13～20 among the embodiment 1.
(battery 51～55)
Make square lithium secondary battery 51～55 with the manufacture method identical with battery 33, different just become 0.5m/min, 1m/min, 2m/min, 5m/min and 8m/min respectively with the flow of the hot-air that forms porous heat-resistant layer in order to dry coated raw material slurry.The porosity of the porous heat-resistant layer of various batteries is 30% (battery 51), 42% (battery 52), 60% (battery 53), 78% (battery 54) or 89% (battery 55).
(battery 56～60)
Use the manufacture method identical to make square lithium secondary battery 56～60 respectively with battery 31～35, the different just thickness of barrier film become 15 μ m and porous heat-resistant layer be not set.
Various batteries carry out twice precharge and discharge, preservation 7 days under 45 ℃ of environment then.Afterwards, with following mode they are assessed.Table 4, table 5 and table 6 have been summarized feature, battery design and the assessment result of porous heat-resistant layer respectively.
(internal short-circuit inspection)
Check the internal short-circuit of these batteries with the method identical with embodiment 1, different just they by following condition charging.The results are shown in Table 6.
Constant current charge: charging current 665mA/ end of charge voltage 4.2V;
Constant voltage charge: charging voltage 4.2V/ charging termination electric current 100mA.
(drop test)
Estimate the anti-drop impact down of these batteries with the method identical with embodiment 1, different just they charge by following condition and discharge.The results are shown in Table 6.
Constant current charge: charging current 665mA/ end of charge voltage 4.2V;
Constant voltage charge: charging voltage 4.2V/ charging termination electric current 100mA;
Constant-current discharge: discharging current 950mA/ final discharging voltage 3V.
After (internal short-circuit inspection after the drop test) drop test, use with drop test before identical method check the internal short-circuit of these batteries.Short circuit incidence after falling the results are shown in Table 6.
(high output characteristic)
Under 20 ℃ of environment, various batteries discharge by following condition and charge, and obtain their discharge capacity.
Constant current charge: charging current 665mA/ end of charge voltage 4.2V;
Constant voltage charge: charging voltage 4.2V/ charging termination electric current 100mA;
Constant-current discharge: discharging current 190mA/ final discharging voltage 3V;
Constant current charge: charging current 665mA/ end of charge voltage 4.2V;
Constant voltage charge: charging voltage 4.2V/ charging termination electric current 100mA;
Constant-current discharge: discharging current 1900mA/ final discharging voltage 3V.
So can obtain the discharge capacity of battery under the 1900mA percentage of its discharge capacity under 190mA relatively.High output characteristic the results are shown in Table 6.
(nail puncture test)
Various batteries charge to the cut-ff voltage of 4.35V under the charging current of 950mA.With the method identical nail is knocked in the battery, and the battery temperature after 90 seconds is assessed with embodiment 1.The results are shown in Table 6.
Table 4
| Battery | Porous heat-resistant layer (μ m) | The position of porous heat-resistant layer | Barrier film (μ m) | Filler | Binder content (wt%) | Porosity (%) |
| 31 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 50 |
| 32 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 50 |
| 33 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 50 |
| 34 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 50 |
| 35 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 50 |
| 36 | 5 | Anodal | 10 | Aluminium oxide | 3 | 50 |
| 37 | 5 | Anodal | 10 | Aluminium oxide | 3 | 50 |
| 38 | 15 | Negative pole | Do not have | Aluminium oxide | 3 | 50 |
| 39 | 5 | Negative pole | 10 | Magnesium oxide | 3 | 50 |
| 40 | 5 | Negative pole | 10 | Silicon dioxide | 3 | 50 |
| 41 | 5 | Negative pole | 10 | Titanium dioxide | 3 | 50 |
| 42 | 5 | Negative pole | 10 | Zirconia | 3 | 50 |
| 43 | 5 | Barrier film | 10 | Aromatic polyamides | 48 | |
| 44 | 5 | Barrier film | 10 | Polyamidoimide | 47 | |
| 45 | 15 | Thin slice independently | Do not have | Aromatic polyamides | 51 | |
| 46 | 15 | Thin slice independently | Do not have | Polyamidoimide | 52 | |
| 47 | 5 | Negative pole | 10 | Aluminium oxide | 0.5 | 61 |
| 48 | 5 | Negative pole | 10 | Aluminium oxide | 1 | 57 |
| 49 | 5 | Negative pole | 10 | Aluminium oxide | 10 | 42 |
| 50 | 5 | Negative pole | 10 | Aluminium oxide | 20 | 35 |
| 51 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 30 |
| 52 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 42 |
| 53 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 60 |
| 54 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 78 |
| 55 | 5 | Negative pole | 10 | Aluminium oxide | 3 | 89 |
| 56 | Do not have | 15 | ||||
| 57 | Do not have | 15 | ||||
| 58 | Do not have | 15 | ||||
| 59 | Do not have | 15 | ||||
| 60 | Do not have | 15 |
Table 5
| Battery | Negative pole width B (mm) | Anodal width (mm) | Design capacity (mAh) | B/A |
| 31 | 43.7 | 42.7 | 950 | 0.950 |
| 32 | 44.6 | 43.6 | 970 | 0.970 |
| 33 | 45 | 44 | 979 | 0.978 |
| 34 | 45.7 | 44.7 | 994 | 0.993 |
| 35 | 46.5 | 45.5 | 1012 | 1.011 |
| 36 | 45 | 44 | 979 | 0.978 |
| 37 | 45.7 | 44.7 | 994 | 0.993 |
| 38 | 45 | 44 | 979 | 0.978 |
| 39 | 45 | 44 | 979 | 0.978 |
| 40 | 45 | 44 | 979 | 0.978 |
| 41 | 45 | 44 | 979 | 0.978 |
| 42 | 45 | 44 | 979 | 0.978 |
| 43 | 45 | 44 | 979 | 0.978 |
| 44 | 45 | 44 | 979 | 0.978 |
| 45 | 45 | 44 | 979 | 0.978 |
| 46 | 45 | 44 | 979 | 0.978 |
| 47 | 45 | 44 | 979 | 0.978 |
| 48 | 45 | 44 | 979 | 0.978 |
| 49 | 45 | 44 | 979 | 0.978 |
| 50 | 45 | 44 | 979 | 0.978 |
| 51 | 45 | 44 | 979 | 0.978 |
| 52 | 45 | 44 | 979 | 0.978 |
| 53 | 45 | 44 | 979 | 0.978 |
| 54 | 45 | 44 | 979 | 0.978 |
| 55 | 45 | 44 | 979 | 0.978 |
| 56 | 43.7 | 42.7 | 950 | 0.950 |
| 57 | 44.6 | 43.6 | 970 | 0.970 |
| 58 | 45 | 44 | 979 | 0.978 |
| 59 | 45.7 | 44.7 | 994 | 0.993 |
| 60 | 46.5 | 45.5 | 1012 | 1.011 |
Table 6
| Battery | Short circuit incidence (%) | Anti-drop impact (%) down | Fall back short circuit incidence (%) | High output characteristic (%) | Nail puncture back battery temperature (℃) |
| 31 | 0 | 93.3 | 1 | 90.4 | 83 |
| 32 | 0 | 98.0 | 0 | 91.2 | 86 |
| 33 | 0 | 99.9 | 0 | 90.1 | 80 |
| 34 | 0 | 99.7 | 0 | 89.4 | 82 |
| 35 | 20 | 98.8 | 0 | 88.9 | 83 |
| 36 | 4 | 99.8 | 3 | 90.2 | 86 |
| 37 | 11 | 99.7 | 12 | 91.3 | 86 |
| 38 | 2 | 99.8 | 13 | 87.8 | 93 |
| 39 | 0 | 99.7 | 0 | 89.1 | 86 |
| 40 | 0 | 99.9 | 0 | 90.1 | 86 |
| 41 | 0 | 99.8 | 0 | 88.9 | 82 |
| 42 | 0 | 99.8 | 0 | 90.4 | 84 |
| 43 | 0 | 99.6 | 10 | 88.8 | 82 |
| 44 | 0 | 99.7 | 11 | 90.1 | 84 |
| 45 | 0 | 99.8 | 12 | 91.2 | 85 |
| 46 | 0 | 99.9 | 11 | 90.7 | 82 |
| 47 | 0 | 99.9 | 8 | 90.4 | 87 |
| 48 | 0 | 99.8 | 0 | 91.4 | 82 |
| 49 | 0 | 99.7 | 0 | 85.3 | 81 |
| 50 | 0 | 99.9 | 0 | 80.3 | 78 |
| 51 | 0 | 96.0 | 0 | 87.7 | 83 |
| 52 | 0 | 99.8 | 0 | 88.2 | 88 |
| 53 | 0 | 100.0 | 0 | 89.4 | 81 |
| 54 | 0 | 99.7 | 0 | 90.0 | 85 |
| 55 | 2 | 99.8 | 14 | 92.1 | 94 |
| 56 | 0 | 99.7 | 0 | 88.4 | 126 |
| 57 | 15 | 99.9 | 0 | 88.9 | 123 |
| 58 | 20 | 99.8 | 0 | 90.2 | 131 |
| 59 | 28 | 99.8 | 0 | 89.1 | 124 |
| 60 | 48 | 99.8 | 5 | 90.1 | 130 |
Relatively from insulator (restriction site) lower surface the battery 31 too small to the distance A of battery case inner bottom surface, capacity density is less in the negative pole width B, and anti-in addition drop impact is lower down.After the drop test, battery 31 taken apart observe, found that the electrode that twines electrode assemblie has taken place to move.
Battery 31 does not have internal short-circuit because of the effect of porous heat-resistant layer, but effective area (anodal and negative pole area respect to one another) reduce to cause its capacitance loss.Because of being furnished with porous heat-resistant layer, its electrode assemblie is anti-deformation, so it can not firmly be fixed on the inboard of battery case.Therefore the electrode that twines electrode assemblie may be moved when repeating.
On the other hand, relatively from the insulator lower surface battery 35 excessive to the distance A of battery case inner bottom surface, anti-short-circuit is lower in the negative pole width B.The sample of determining to be in the battery 35 of internal short-circuit attitude taken apart observe.Found that the porous heat-resistant layer on the negative terminal surface has damage at the first half of electrode assemblie.Find that also barrier film ftractures.
In the ratio of B/A was 0.975～0.995 battery 33～34, anti-short-circuit was higher, and anti-in addition drop impact down is improved.Battery of the present invention also is furnished with porous heat-resistant layer except that barrier film is arranged.Therefore, though when negative pole than anodal wide, when the electrode assemblie first half has slight deformation, the double-decker of being made up of porous heat-resistant layer and barrier film insulate crushed element.In addition, because the ratio of B/A is higher, electrode assemblie firmly is clipped between the inner bottom surface of the surface of insulator Lower Half and battery case.Therefore the anti-drop impact down of battery may be improved.
Yet in the ratio of B/A was 0.965～0.975 battery 32, anti-drop impact down was a little less than the anti-drop impact down of the cylindrical battery 2 (embodiment 1) of the B/A with same ratio scope.With regard to cylindrical battery, the cross section of its slot part (restriction site) be approximate V-arrangement or U-shaped.Therefore, the top of electrode assemblie is pushed down by the slope of slot part.On the other hand, with regard to square lithium secondary battery, the surface of insulator (restriction site) Lower Half is flat, does not therefore have the slope as slot part.Therefore various batteries may exist above-mentioned difference in more efficiently B/A ratio range.
In the battery 56～60 that does not have porous heat-resistant layer, the anti-influence of position, the unrestricted position of drop impact down all is good.It is believed that, because of the electrode assemblie that does not have porous heat-resistant layer is deformed to an appropriate level, so it firmly is fixed in the battery case.Even when these batteries fall, cause the electrode of the winding electrode assemblie of capacitance loss to move and therefore to be suppressed.Yet these batteries 56～60 are obviously overheated in nail puncture test.In addition, in identical with battery 32～34 respectively battery 57～59 in restriction site position, anti-short-circuit is lower.It is believed that the negative pole of these batteries 57～59 has slight deformation.Yet because these batteries do not have porous heat-resistant layer, when barrier film because of negative pole deformation cracking took place, internal short-circuit can not prevent.
In battery 36 and 37, porous heat-resistant layer is formed on the surface of anode active material layer.In these two kinds of batteries, the battery 37 with wideer negative pole demonstrates relatively low anti-short-circuit.This may be because porous heat-resistant layer is formed on the surface of the anode active material layer narrower than anode active material layer, so negative terminal surface is touched with anodal first half side edge at the first half of electrode assemblie.
In the battery 38 that does not have barrier film, the following anti-short-circuit that falls behind is lower slightly.More frangible on the porous heat-resistant layer structure than barrier film.So, porous heat-resistant layer fallen percussion and local damage, thus be short-circuited.
Have in the battery 43 and 44 of the porous heat-resistant layer of being made by heat stable resin at membrane surface, the following anti-short-circuit that falls behind is lower slightly.The mechanical strength of the porous heat-resistant layer that heat stable resin is made is lower than the mechanical strength of the porous heat-resistant layer that comprises insulating packing and adhesive.So short circuit takes place by the whereabouts percussion.
Have independently the porous heat-resistant layer thin slice and do not having in the battery 45 and 46 of barrier film, the anti-short-circuit after the anti-short-circuit after they fall is lower than battery 43 and battery 44 and falls.This comes from this fact, and promptly the intensity of porous heat-resistant layer intensity difference of being made by heat stable resin and porous heat-resistant layer is not improved because of lacking of barrier film.
Contain in porous heat-resistant layer in the battery 47 of 0.5wt% adhesive, the anti-short-circuit after falling is lower slightly.This may be because the adhesive of low content has weakened the adhesion of filler grain, thereby causes the mechanical strength of porous heat-resistant layer relatively poor.
On the other hand, in the battery 50 that contains the 20wt% adhesive, high output characteristic is lower slightly.This may be because excessive adhesive has reduced the porosity of porous heat-resistant layer, and in addition, excessive adhesive is with the electrolyte swelling, thereby makes the micropore of porous heat-resistant layer closed and reduced ionic conductivity.On the other hand, be in the battery 48～49 of 1wt%～10wt% at binder content, anti-short-circuit and high output characteristic all are good.
In the battery 51 of the porous heat-resistant layer that has 30% porosity that obtains because of the control drying condition, anti-drop impact is lower slightly down.Its reason may be as follows.Because porosity is low, porous heat-resistant layer is not soaked into electrolyte fully, so the swelling of electrode assemblie is less.Therefore, can not prevent that electrode assemblie from moving when falling.In the battery 55 of the porous heat-resistant layer with 89% porosity, the anti-short-circuit after falling is lower slightly.This may be because the mechanical strength of porous heat-resistant layer is relatively poor.
On the other hand, in having the battery 52～54 that porosity is 40%～80% porous heat-resistant layer, anti-drop impact down and fall after anti-short-circuit all be good.Its reason may be as follows.Because optimized porosity, the mechanical strength of porous heat-resistant layer is maintained.In addition, porous heat-resistant layer swells to an appropriate level with electrolyte.So prevented moving of electrode assemblie.
Industrial applicibility
Because lithium secondary battery of the present invention has outstanding Short Circuit withstand and heat resistance and high security and can be because not impacting as fall capacitance loss be arranged, thus can be used as the power supply of any mancarried device, such as personal digital assistant and portable electric appts. Lithium secondary battery of the present invention can be used as the power supply such as home-use small-sized electrical storage device, two-wheeled vehicle, electric motor car and dual-purpose electric car, and purposes of the present invention is not particularly limited.
Claims (13)
1. a lithium secondary battery comprises: have bottom, sidewall and open-topped battery case; Electrode assemblie; Nonaqueous electrolytic solution; And cover open-topped sealing plate in order to the described battery case that holds described electrode assemblie and described electrolyte,
It is characterized in that, described electrode assemblie comprises and is inserted in the anodal and bar shaped negative pole of bar shaped that the porous heat-resistant layer between positive pole and the negative pole is intertwined, described positive pole comprises anodal core components and the anode active material layer that is coated on the anodal core components two sides, described negative pole comprises negative pole core components and the anode active material layer that is coated on the negative pole core components two sides
Described battery has the restriction site of the described electrode assemblie vertical moving of restriction, satisfies relational expression: 0.965≤B/A≤0.995 distance A from described restriction site to described battery case inner bottom surface and the width B of described negative pole,
Described porous heat-resistant layer contains insulating packing and adhesive, and
Described porous heat-resistant layer has 40%～80% porosity and the thickness of 0.5～20 μ m.
2. lithium secondary battery as claimed in claim 1 is characterized in that, further comprises the barrier film that contains microporous barrier, and described barrier film is inserted between described porous heat-resistant layer and the described positive pole or between described porous heat-resistant layer and described negative pole.
3. lithium secondary battery as claimed in claim 1 is characterized in that, described porous heat-resistant layer is formed in described anode active material layer and the described anode active material layer on the surface of at least one.
4. lithium secondary battery as claimed in claim 1 is characterized in that described insulating packing comprises inorganic oxide.
5. lithium secondary battery as claimed in claim 4 is characterized in that, described inorganic oxide comprises and is selected from least a in aluminium oxide, silicon dioxide, magnesium oxide, titanium dioxide and the zirconia.
6. lithium secondary battery as claimed in claim 1 is characterized in that, is benchmark with the described insulating packing of 100 weight portions, and the amount of described adhesive is 1～10 weight portion.
7. lithium secondary battery as claimed in claim 1 is characterized in that, described electrode assemblie is cylindrical, and described battery case is a cylindrical shape, and described restriction site is the slot part that makes the described battery case that internal diameter reduces that is positioned at the battery case side wall upper part.
8. lithium secondary battery as claimed in claim 1, it is characterized in that, further comprise the insulator between described electrode assemblie and described sealing plate, wherein said electrode assemblie is that the cross section is the cylindrical of ellipse, described battery case is prismatic, and described restriction site is the lower surface of insulator.
9. lithium secondary battery as claimed in claim 7 is characterized in that, satisfies relational expression: 0.970≤B/A≤0.990 distance A of the inner surface from described restriction site to described battery case bottom and the width B of described negative pole.
10. lithium secondary battery as claimed in claim 8 is characterized in that, satisfies relational expression: 0.975≤B/A≤0.990 distance A of the inner surface from described restriction site to described battery case bottom and the width B of described negative pole.
11. lithium secondary battery as claimed in claim 8 is characterized in that, satisfies relational expression: 0.975≤B/A≤0.995 distance A of the inner surface from described restriction site to described battery case bottom and the width B of described negative pole.
12. lithium secondary battery as claimed in claim 1 is characterized in that, is benchmark with the described insulating packing of 100 weight portions, the amount of described adhesive is 2～8 weight portions.
13. lithium secondary battery as claimed in claim 1 is characterized in that, described porous heat-resistant layer has 40%～65% porosity.
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| US20100227210A1 (en) * | 2008-06-02 | 2010-09-09 | Masao Fukunaga | Non-aqueous electrolyte secondary battery and method for manufacturing the same |
| US20110165445A1 (en) * | 2009-01-29 | 2011-07-07 | Yoshiyuki Muraoka | Nonaqueous electrolyte secondary battery and method for fabricating the same |
| CN102142542B (en) * | 2010-01-29 | 2013-09-18 | 上海比亚迪有限公司 | Method for preparing electrode |
| CN102222787A (en) * | 2010-04-15 | 2011-10-19 | 深圳市比克电池有限公司 | Lithium ion battery electrode plate, battery and method for improving battery security |
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| CN111868966A (en) * | 2018-03-13 | 2020-10-30 | 三洋电机株式会社 | Secondary battery |
| JP7011045B2 (en) * | 2018-03-28 | 2022-02-10 | 株式会社東芝 | Rechargeable batteries, battery modules, vehicles and projectiles |
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| CN105830250A (en) * | 2013-12-11 | 2016-08-03 | 丰田自动车株式会社 | Rectangular secondary battery |
| CN105830250B (en) * | 2013-12-11 | 2018-09-18 | 丰田自动车株式会社 | Non-aqueous electrolyte secondary battery |
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