CN100431216C - Lithium ion secondary battery - Google Patents
Lithium ion secondary battery Download PDFInfo
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- CN100431216C CN100431216C CNB200580014042XA CN200580014042A CN100431216C CN 100431216 C CN100431216 C CN 100431216C CN B200580014042X A CNB200580014042X A CN B200580014042XA CN 200580014042 A CN200580014042 A CN 200580014042A CN 100431216 C CN100431216 C CN 100431216C
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Abstract
Disclosed is a lithium ion secondary battery comprising a positive electrode containing a lithium complex oxide, a negative electrode capable of charging/discharging lithium ions, a nonaqueous electrolyte solution, and a solid electrolyte layer interposed between the positive electrode and the negative electrode. The solid electrolyte layer contains solid electrolyte particles and a binder, and may further contain an inorganic oxide filler. For example, the solid electrolyte particles are composed of at least one material selected from the group consisting of LiCl-Li2O-P2O5, LiTi2(PO4)3-AlPO4, LiI-Li2S-SiS4, LiI-Li2S-B2S3, LiI-Li2S-P2O5 and Li3N.
Description
Technical field
The lithium rechargeable battery of the present invention relates to have excellent charge, preventing the high safety of short circuit and heat resistance.
Background technology
For example the chemical cell of lithium rechargeable battery comprises the barrier film between positive pole and negative pole, and it is used for providing electric insulation and is used for keeping electrolyte between each battery lead plate.The at present main microporous membrane sheet that comprises poly resin for example that uses is as barrier film.But the diaphragm that comprises resin trends towards the thermal contraction owing to the reaction heat that comes from short circuit that produces immediately usually when internal short-circuit.For example, when as nail have the outstanding object penetration battery of sharp shape the time, the part of short circuit may expand, and then produces a large amount of reaction heat, thereby has quickened the temperature in the battery and risen.
In order to improve the fail safe of battery, advised on the surface of negative or positive electrode, forming porous protection film, comprise for example inorganic solid particles and the resinoid bond (for example referring to patent documentation 1) of aluminium oxide.Advised that also the glass ceramics that will have lithium-ion-conducting is used for electrolyte (for example referring to patent documentation 2).
Patent documentation 1
TOHKEMY Hei 7-220759 number
TOHKEMY 2000-26135 number
Summary of the invention
The problem to be solved in the present invention
For example the inorganic solid particles of aluminium oxide or resinoid bond do not have ionic conductivity.Therefore, on electrode surface, form in the situation of diaphragm of the inorganic solid particles comprise aluminium oxide for example and resinoid bond, consider, need be arranged to the porosity of diaphragm high from the angle of keeping charge.When the porosity of diaphragm hangs down, be packed into electrolytical space and reduce, thereby suppressed ionic conduction.But, to be arranged to when high when the porosity of diaphragm, the strength reduction of perforated membrane causes short circuit etc., thereby can not realize improving the effect of battery security.That is, there are the balance relation in charge and fail safe, and are difficult to realize simultaneously both.
Be used for electrolytical situation in the glass ceramics with lithium-ion-conducting, because glass ceramics is a solid, the fail safe of battery improves satisfactorily.But because compare with the electrolyte that comprises organic nonaqueous solvents, the ionic conductivity of glass ceramics is not enough, so be difficult to guarantee charge.
Therefore, the objective of the invention is to provide charge and the in the past safer lithium rechargeable battery of ratio with excellence by the layer that between positive pole and negative pole, inserts ionic conductivity and excellent heat resistance.
The method of dealing with problems
The present invention relates to lithium rechargeable battery, it comprises: the positive pole that comprises lithium composite xoide; Can charge into and discharge the negative pole of lithium ion; Non-aqueous electrolyte; And being inserted in solid electrolyte layer between positive pole and the negative pole, wherein said solid electrolyte layer comprises solid electrolyte particle and binding agent.
Solid electrolyte particle has ionic conductivity, and they are solid-state.The migration of ion in solid electrolyte is different from the ion of the solvation of moving in liquid electrolyte.Because ion is at the solid electrolyte internal motion, so exist or do not exist space or liquid electrolyte can not influence the ionic conductivity of solid electrolyte.In addition, between positive pole and negative pole, have nonaqueous electrolyte, and ion migration do not depend on solid electrolyte, thereby guarantee charge easily.
Preferred solid electrolyte particle comprises and is selected from least a in following group: LiCl-Li
2O-P
2O
5(comprise LiCl, Li
2O and P
2O
5Glassy composition), LiTi
2(PO
4)
3-AlPO
4(comprise LiTi
2(PO
4)
3And AlPO
4Glassy composition), LiI-Li
2S-SiS
4(comprise LiI, Li
2S and SiS
4Glassy composition), LiI-Li
2S-B
2S
3(comprise LiI, Li
2S and B
2S
3Glassy composition), LiI-Li
2S-P
2O
5(comprise LiI, Li
2S and P
2O
5Glassy composition) and Li
3N.In addition, preferably regulate the glassy composition in each composition, make that lithium ion conductivity is 10
-2-10
-4S/cm.
Solid electrolyte layer can comprise the inorganic oxide filler.
Hybrid solid electrolyte particle and inorganic oxide filler have improved the liquid electrolyte reserve capability of solid electrolyte layer, still become easily with liquid electrolyte impregnated electrode group, can reduce cost in addition.Should be understood that the electrode group is by twining or stacked positive pole and negative pole obtain.By using liquid electrolyte impregnated electrode group to become easily, can reduce the operating time of manufacturing.In addition, will improve aspect the performance degradation that causes by exhausting of electrode surface, and therefore improve life characteristic.In addition, suppressed on electrode surface, to produce big Schottky barrier, thereby be convenient to the ion migration and kept charge.
Herein, solid electrolyte refers to have " lithium-ion-conducting " and is solid-state electrolyte at normal temperatures, and the inorganic oxide filler refers to not have the inorganic oxide particles of " lithium-ion-conducting ".
The consumption of the inorganic oxide filler that comprises in the solid electrolyte layer is preferably to be no more than 100 weight portions in per 100 weight portion solid electrolyte particles, and especially preferably is not less than 50 weight portions and is no more than 99 weight portions.When the amount of inorganic oxide filler is too big, may be difficult to improve the charge of battery.
Preferred solid electrolyte and anodal surface and negative terminal surface bond one of at least.By solid electrolyte layer is bonded on the electrode surface, can prevent that solid electrolyte layer from shrinking simultaneously when barrier film (microporous membrane that comprises resin) thermal contraction.
Preferred inorganic oxide filler comprises and is selected from least a in titanium oxide, zirconia, aluminium oxide and the magnesium oxide.Reason is that they have excellent electrochemical stability.
The binding agent that comprises in the preferred solid electrolyte layer comprises the rubber-like polymer that comprises acrylonitrile unit at least.Reason is that the rubber-like polymer that comprises acrylonitrile unit provides pliability to solid electrolyte layer, and therefore is convenient to form the electrode group.
Preferred solid electrolyte particle has the flakey shape.Use has the solid electrolyte particle of flakey shape, can prevent to produce in solid electrolyte layer uneven space (hole or through hole).
When solid electrolyte particle is when having the flakey shape of major axis and minor axis, preferred solid electrolyte particle has the major axis that is not less than 0.1 μ m and is not more than 3 μ m.Should be understood that major axis is meant the Breadth Maximum of particle.When use has major axis less than the particle of the flakey shape of 0.1 μ m, the filling rate of solid electrolyte particle in solid electrolyte layer uprises, thereby may need the long time with liquid electrolyte impregnated electrode group, the feasible operating time (tact time) that is difficult to reduce in the manufacturing.When the major axis of particle during, when solid electrolyte layer forms thinlyyer, be easy to generate uneven space when for example being no more than the thickness of 6 μ m greater than 3 μ m with flakey shape.
Preferred solid electrolyte layer has the thickness that is not less than 3 μ m and is no more than 30 μ m.When the thickness of solid electrolyte layer during less than 3 μ m, may produce leakage current, and when it was thicker than 30 μ m, internal resistance increased, make to be difficult to the battery capacity that provides high.
In lithium rechargeable battery of the present invention, can between positive pole and negative pole, further insert polyolefin layer.Herein, polyolefin layer comprises polyolefin particles.The preferred use is selected from least a as described polyolefin particles in polyethylene particle and the polypropylene GRANULES.The preferred polyolefm layer comprises binding agent.
The internal temperature of lithium rechargeable battery may increase near 140 ℃ when overcharging, although this depends on the composition of electrode.When the internal temperature of battery increased, polyolefin melted under lower temperature, and therefore as the release mechanism of interruptive current (promptly physically interrupting the ion migration).In addition, polyolefin can tolerate the environment of inside battery.
Polyolefin layer can bond one of at least with anodal surface and negative terminal surface.
For instance, the present invention includes following content.
(i) a kind of lithium rechargeable battery, wherein solid electrolyte layer and negative terminal surface bonding, and the surface of polyolefin layer and solid electrolyte layer bonding.
(ii) a kind of lithium rechargeable battery, wherein polyolefin layer and negative terminal surface bonding, and the surface of solid electrolyte layer and polyolefin layer bonding.
(iii) a kind of lithium rechargeable battery, wherein polyolefin layer and negative terminal surface bonding, and solid electrolyte layer and anodal surface bonding.
(iv) a kind of lithium rechargeable battery, wherein solid electrolyte layer bonds with anodal surface, and the surface of polyolefin layer and solid electrolyte layer bonding.
When making lithium rechargeable battery, negative pole can obtain with the shorter operating time.Therefore, as described in above-mentioned (i), it is favourable forming solid electrolyte layer with regard to the manufacturing operation time on negative terminal surface.In addition, form solid electrolyte layer with the paste that comprises solid electrolyte particle and binding agent.Therefore, at first on negative terminal surface, forming solid electrolyte layer, forming then in the situation of polyolefin layer, can prevent that the decentralized medium that comprises in the paste suppressing agent or binding agent immerse in the space between polyolefin particles, thereby can prevent the reduction of reproducibility.
Consider from effective life characteristic angle of improving lithium rechargeable battery, as above-mentioned (ii) as described in, it is favourable forming polyolefin layer on negative terminal surface.Reason is to form polyolefin layer can prevent that polyolefin is by anodal oxidation on negative terminal surface.
The manufacturing reproducibility of collateral security lithium rechargeable battery and the life characteristic angle of effectively improving lithium rechargeable battery consider, as above-mentioned (iii) as described in, be favourable forming polyolefin layer on the negative terminal surface and on anodal surface, forming solid electrolyte layer.Reason is in the decentralized medium or the space between the polyolefin particles in the binding agent immersion polyolefin layer that the formation solid electrolyte layer can be prevented comprising in the paste suppressing agent on anodal surface, prevents oxidation of polyolefins simultaneously.
The manufacturing reproducibility of collateral security lithium rechargeable battery is also effectively improved the life characteristic of lithium rechargeable battery, and the angle that further reduces the manufacturing operation time is considered, as above-mentioned (iv) as described in, be favourable forming solid electrolyte layer on the anodal surface and on the solid electrolyte laminar surface, forming polyolefin layer.
Effect of the present invention
By the present invention, can obtain the lithium rechargeable battery of the high safety of charge, anti-short circuit and excellent heat resistance effectively.
Description of drawings
Fig. 1 is the vertical cutaway view according to the cylindrical lithium ion secondary battery of the embodiment of the invention.
Embodiment
Lithium rechargeable battery according to the present invention comprises the positive pole that comprises lithium composite xoide, the negative pole and the non-aqueous electrolyte that can charge into and discharge lithium ion, wherein between positive pole and negative pole, insert solid electrolyte layer, and further insert polyolefin layer betwixt.Preferred solid electrolyte layer comprises solid electrolyte particle and binding agent, and polyolefin layer comprises polyolefin particles, specifically is selected from polyethylene particle and the polypropylene GRANULES at least a.The preferred polyolefm layer also comprises binding agent.The binding agent that comprises in the binding agent that comprises in the solid electrolyte layer and the polyolefin layer can be identical or different.Lithium rechargeable battery according to the present invention may further include between positive pole and negative pole or does not comprise barrier film (microporous membrane sheet).
It is enough having solid electrolyte layer between positive pole and negative pole.The present invention includes all following situations: the situation of solid electrolyte layer and anodal surface bonding, the situation that it bonds with the surface of the situation of negative terminal surface bonding and it and polyolefin layer.Similarly, the present invention includes all following situations: the situation of polyolefin layer and anodal surface bonding, the situation that it bonds with the surface of the situation of negative terminal surface bonding and it and solid electrolyte layer.But, consider from the angle that prevents oxidation of polyolefins, preferably polyolefin layer is arranged to positive pole and does not contact each other with polyolefin layer.
For solid electrolyte particle, for example can use glass with ionic conductivity.Wherein, preferably use LiCl-Li
2O-P
2O
5, LiTi
2(PO
4)
3-AlPO
4, LiI-Li
2S-SiS
4, LiI-Li
2S-B
2S
3, LiI-Li
2S-P
2O
5, Li
3N etc.These materials are effectively for ionic conduction, and are the most effective for lithium ion conduction.Usually, material in addition has bad lithium-ion-conducting, and may cause energy loss.But the material except above-mentioned material also may provide effect of the present invention.
Although it is the shape for solid electrolyte particle is not particularly limited, for example preferably bulk, spherical, fibrous or lepidiod, and especially preferably lepidiod.When solid electrolyte particle has the flakey shape, can obtain the uniform solid electrolyte layer that solid electrolyte particle evenly is orientated in one direction.As if in addition, particle is sprawled as tile, and therefore trend towards can not forming through hole in solid electrolyte layer.
Major axis with solid electrolyte particle of flakey shape preferably on average is not less than 0.1 μ m and is no more than 3 μ m.When major axis during less than 0.1 μ m, need the long time with liquid electrolyte impregnated electrode group, and when major axis surpasses 3 μ m, when for example being no more than the solid electrolyte layer of less thickness of 6 μ m, formation may produce uneven space.
Although be not particularly limited for the binding agent that comprises in solid electrolyte layer or the polyolefin layer, but for example can use polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene butadiene ribber (SBR), the modification SBR that comprises acrylic acid units or acrylic ester unit, polyethylene, polyacrylic acid radical derivative rubber (BM-500B (trade (brand) name), produce by ZEON Corporation) and the acrylic-nitrile rubber (BM-720H (trade (brand) name) is by ZEON Corporation production) of modification.These binding agents can be separately or with its two or more be used in combination.Wherein, the acrylic-nitrile rubber of modification is particularly preferred.
The acrylic-nitrile rubber of modification is the rubber-like polymer that comprises acrylonitrile unit, and has the feature of amorphous and high-fire resistance.When twining positive pole and the negative pole that is inserted with solid electrolyte layer therebetween, the solid electrolyte layer that comprises this binding agent trends towards can not causing crackle etc., and therefore can keep the high productivity ratio of lithium rechargeable battery.
Except acrylonitrile unit, the rubber-like polymer that comprises acrylonitrile unit can comprise be selected from methyl acrylate unit, ethyl acrylate unit, methyl methacrylate units and the EMA unit one of at least.In addition, it can also comprise: alkyl acrylate, for example acrylic acid n-propyl, isopropyl acrylate, acrylic acid tertiary butyl ester, Hexyl 2-propenoate, cyclohexyl acrylate, acrylic acid dodecane ester or lauryl acrylate; Alkyl methacrylate, for example n propyl methacrylate, isopropyl methacrylate, methacrylic acid tertiary butyl ester, hexyl methacrylate, cyclohexyl methacrylate, methacrylic acid dodecane ester or lauryl methacrylate; Unsaturated polycarboxylic acid's Arrcostab, for example dimethyl fumarate, diethyl maleate or butyl benzene citraconic acid ester; The esters of unsaturated carboxylic acids that comprises alkoxyl, for example, acrylic acid 2-methoxy ethyl ester or methacrylic acid 2-methoxy ethyl ester; Perhaps α, β-undersaturated nitrile, for example acrylonitrile or methacrylonitrile.
Preferably ceramic material is used for the inorganic oxide filler that solid electrolyte layer comprises.Reason is that ceramic material has high thermal endurance, is electrochemical stability in the inside battery environment, and also is fit to be used for preparing paste.As inorganic oxide, for example the aluminium oxide of Alpha-alumina, titanium oxide, zirconia, magnesium oxide etc. are most preferred aspect electrochemical stability.
Although the average grain diameter for the inorganic oxide filler that comprises in the solid electrolyte layer is not particularly limited, its 0.1-6 μ m preferably for instance.Although the average grain diameter for the polyolefin particles that comprises in the polyolefin layer is not particularly limited, its 0.1-3 μ m preferably for instance.For example can measure these average grain diameters with the wet type laser particle size distribution measuring equipment that Microtrac Inc. makes.In the case, can be with the value (intermediate value: D of 50% on the packing volume basis
50) regard the average grain diameter of filler as.
When solid electrolyte layer did not comprise the inorganic oxide filler, the content of the solid electrolyte particle in the solid electrolyte layer preferably was not less than 50 weight % and is no more than 99 weight %, and more preferably was not less than 66 weight % and is no more than 96 weight %.Therefore, the content of the binding agent in the solid electrolyte layer preferably is not less than 1 weight % and is no more than 50 weight %.
When solid electrolyte layer comprises the inorganic oxide filler, the total content of solid electrolyte particle in the solid electrolyte layer and inorganic oxide filler preferably is not less than 50 weight % and is no more than 99 weight %, and more preferably is not less than 66 weight % and is no more than 96 weight %.But for per 100 weight portion solid electrolyte particles, the content of inorganic oxide filler preferably is no more than 100 weight portions.
The content of polyolefin particles preferably is not less than 50 weight % and is no more than 99 weight % in the polyolefin layer, and more preferably is not less than 60 weight % and is no more than 96 weight %.Therefore, the content of binding agent preferably is not less than 1 weight % and is no more than 50 weight % in the polyolefin layer.
In addition, when the granule content in every layer during less than 50 weight %, particle can not play one's part to the full, and the microcellular structure in being difficult to control every layer.On the other hand, when the granule content in every layer surpassed 99 weight %, every layer intensity had the trend of reduction.Should be understood that can form multilayer has different solid electrolyte layer or the polyolefin layers of forming.
Preferably, use lithium composite xoide, use the material that can charge into and discharge lithium ion, and use the nonaqueous solvents that dissolves lithium salts as non-aqueous electrolyte for negative pole for positive pole.
For example, the preferred transition metal oxide that contains lithium that uses, for example cobalt acid lithium, lithium nickelate and LiMn2O4 are as lithium composite xoide.The also preferred product that wherein partly replaces the modification of the transition metal in the lithium-containing transition metal oxide that uses with another kind of element.For example, excellent aluminium, magnesium etc. replace the cobalt in the cobalt acid lithium, and preferably with the nickel in the cobalt replacement lithium nickelate.Lithium composite xoide can be separately or with its two or more be used in combination.
The example that can charge into and discharge the material of lithium ion that is used for negative pole comprises various native graphites, various Delanium, silicon based composite material and various alloy material.These materials can be separately or with its two or more be used in combination.
Usually, anodal and negative pole comprises binders for electrodes.For binders for electrodes, for example can use polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene butadiene ribber (SBR), polyacrylic acid radical derivative rubber (BM-500B (trade (brand) name), produce by ZEON Corporation) and the acrylic-nitrile rubber (BM-720H (trade (brand) name) is by ZEON Corporation production) of modification.They can be separately or with its two or more be used in combination.
Binders for electrodes can be used in combination with thickener.For example can use the acrylic-nitrile rubber (by the BM-720H of ZEONCorporation production) of carboxymethyl cellulose (CMC), poly(ethylene oxide) (PEO) and modification.These binding agents can be separately or with its two or more be used in combination.
Usually, positive pole comprises conductive agent.For example can use carbon black (for example acetylene black and Kai Jinhei) and various graphite as conductive agent.These materials can be separately or with its two or more be used in combination.
Although be not particularly limited, can use for instance: carbonic ester, for example ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethylene methyl esters (EMC) for nonaqueous solvents; Carboxylate, for example gamma-butyrolacton, gamma-valerolactone, methyl formate, methyl acetate and methyl propionate; And ether, for example dimethyl ether, diethyl ether and oxolane.Nonaqueous solvents can be separately or with its two or more be used in combination.Wherein, it is particularly preferred using carbonic ester.
Although be not particularly limited, preferably use LiPF for instance for lithium salts
6, LiBF
4Deng.These lithium salts can be used alone or in combination.
In order when overcharging, to guarantee stability, preferably in nonaqueous electrolyte, add minor amounts of additives, for example vinylene carbonate (VC), vinylethylene carbonate (VEC) or cyclohexylbenzene (CHB), thus good film on positive pole and/or negative pole, formed.
When lithium rechargeable battery of the present invention comprised the microporous membrane sheet as barrier film, preferably this microporous membrane sheet comprised vistanex.Vistanex has repellence for the environment of inside battery, and the function of sealing can be provided barrier film.Closing function is when battery temperature becomes high owing to some defective, and barrier film melts and close the function of its micropore.This has cut off the ion channel by liquid electrolyte, thereby has kept the fail safe of battery.For instance, comprise the monofilm of polyvinyl resin or acrylic resin and comprise that multilayer film two-layer or the multi-layer polyolefin resin is suitable as described microporous membrane sheet.Although the thickness for barrier film is not particularly limited, it is 5-20 μ m for instance.Use barrier film to make and more difficultly cause short circuit, thereby improved the fail safe and the reliability of lithium rechargeable battery.
Although the thickness for solid electrolyte layer is not particularly limited, for example collateral security improves the effect of fail safe and the design capacity angle of assurance battery considers that it preferably is not less than the thickness of 3 μ m and is no more than 30 μ m.Although the thickness for polyolefin layer is not particularly limited, for example collateral security improves the effect of fail safe and the design capacity angle of assurance battery considers that it preferably is not less than the thickness of 3 μ m and is no more than 30 μ m.For instance, when also using barrier film, wait to determine the concrete thickness of these layers in the liquid electrolyte reserve capacity of consideration barrier film and the consideration manufacture process with the speed of liquid electrolyte impregnated electrode group.
When lithium rechargeable battery did not comprise the microporous membrane sheet as barrier film, the thickness of solid electrolyte layer or polyolefin layer preferably was not less than 10 μ m and is no more than 30 μ m.When lithium rechargeable battery comprised the microporous membrane sheet as barrier film, the thickness of solid electrolyte layer or polyolefin layer preferably was not less than the thickness of 3 μ m and is no more than 15 μ m.In addition, consider that from the design capacity angle of keeping battery the gross thickness of solid electrolyte layer, polyolefin layer and barrier film preferably is set to 15-30 μ m.
Although be not particularly limited for the method that forms solid electrolyte layer or polyolefin layer, but for instance, to comprise the paste of solid electrolyte particle and binding agent or comprise polyolefin particles and the paste of binding agent is coated on the active material layer of original electrode slice that comprises collector body and load on the active material layer on the collector body, then dry.Although preferred, be not limited to these methods by selecting the coating of enforcement pastes such as rolling method, intaglio printing roller coat method, mold pressing coating process.Should be understood that original electrode slice is meant the precursor of battery lead plate before cutting into reservation shape according to battery size.
By being mixed together solid electrolyte particle and binding agent, obtain to comprise the paste of solid electrolyte particle and binding agent with liquid component (decentralized medium).Although can make water, NMP or cyclohexanone as liquid component for instance, be not limited to this.Use double arm kneading mixer (for example planetary-type mixer) or wet dispersion machine (for example pearl mill) to carry out the mixing of solid electrolyte particle, binding agent and decentralized medium.Also obtain to comprise the paste of polyolefin particles and binding agent according to identical method.
Hereinafter, the present invention is described, but these embodiment are intended to set forth according to lithium rechargeable battery of the present invention, and do not plan to limit the present invention by embodiment.
Comparing embodiment 1
(i) Zheng Ji preparation
By using double arm kneading mixer to stir 3kg cobalt acid lithium (LiCoO with the N-N-methyl-2-2-pyrrolidone N-(NMP) of appropriate amount
2: positive electrode active materials), 120g PVDF (anodal binding agent:, prepare positive electrode mixture paste the solid constituent of the PVDF#1320 (trade (brand) name) that produces by KUREHA CORPORATION) and 90g acetylene black (anodal conductive agent).This paste is administered on the both sides of the thick aluminium foil of 15 μ m, then dry to obtain the former base of positive plate.The former base of this positive plate is rolled the thickness that becomes to have 160 μ m, cut into then and have the width that can insert in the 18650 type cylindrical battery shells, thereby obtain anode ring.
The (ii) preparation of negative pole
The solid constituent of the BM-400B (trade (brand) name) that produces by ZEONCorporation) and 30g carboxymethyl cellulose (CMC: thickener), prepare negative material mixture paste by using double arm kneading mixer to stir 3kg Delanium (negative active core-shell material), 30g styrene butadiene rubbers (negative pole binding agent: with the water of appropriate amount.This paste is administered on the both sides of the thick Copper Foil of 10 μ m, then dry to obtain the former base of negative plate.The former base of this negative plate is rolled the thickness that becomes to have 180 μ m, cut into then and have the width that can insert in the 18650 type cylindrical battery shells, thereby obtain the negative pole ring.
Using above-mentioned anode ring and negative pole ring manufacturing production number as shown in Figure 1 is 18650 cylindrical battery.
Each all is cut into predetermined length to obtain anodal 5 and negative pole 6 with anode ring and negative pole ring.The end of positive wire 5a is connected with anodal 5, and the end of negative wire 6a is connected with negative pole 6.Twine positive pole 5 and negative pole 6, arrange the microporous membrane sheet of making and having 20 μ m thickness by polyvinyl resin therebetween, thereby construct the electrode group.By being clipped between dead ring 8a and the following dead ring 8b and this electrode group is inserted in cylindrical 18650 battery cases 1, then to wherein injecting the 5.5g non-aqueous electrolyte.
By concentration of ordinary dissolution in the mixed solvent that comprises 2: 3: 3 ethylene carbonate of volume ratio, dimethyl carbonate and ethylene methyl esters is the LiPF of 1mol/L
6, and dissolve the vinylene carbonate of 3 weight % more therein, obtain non-aqueous electrolyte.
The other end of positive wire 5a is soldered on the back side of battery cover 2, and the other end of negative wire 6a is soldered on the inner bottom surface of battery case 1.At last, with the opening of battery cover 2 sealed cell shells 1, battery cover comprises and is arranged in its peripheral insulation cushion 3.Thus, make cylindrical lithium ion secondary battery.
Embodiment 1
Except on the both sides of negative pole ring, forming solid electrolyte layer, and with glassy composition (by the YC-LC powder (trade (brand) name) that OHARA INC. produces, major axis is 1 μ m, and consists of: LiCl-Li
2O-P
2O
5) be used to have outside the solid electrolyte particle of flakey shape and ionic conductivity, make cylindrical lithium ion secondary battery according to the method identical with comparing embodiment 1.
Specifically, stir the acrylic-nitrile rubber (solid constituent of the BM-720H (trade (brand) name) that produces by ZEON Corporation) of 970g solid electrolyte particle, 30 g modifications and the NMP of appropriate amount, prepare paste by using double arm kneading mixer.Except this paste being administered on the both sides of negative pole ring, then dry, to form in every side outside the thick solid electrolyte layer of 5 μ m, implement and comparing embodiment 1 identical operations.
Except the thickness of every side solid electrolyte layer being changed into the 20 μ m, on the both sides of negative pole ring, form solid electrolyte layer according to the method identical with embodiment 1.In addition, except using this negative pole ring, and do not use outside the barrier film, make cylindrical lithium ion secondary battery according to the method identical with comparing embodiment 1.
Except (by the YC-LC powder (trade (brand) name) that OHARA INC. produces, major axis is 1 μ m, and consists of: LiCl-Li with glassy composition
2O-P
2O
5) be used to have the solid electrolyte particle of flakey shape and ionic conductivity, and with average grain diameter is that the Alpha-alumina of 0.3 μ m is used for the inorganic oxide filler, come on the both sides of negative pole ring, to form outside the solid electrolyte layer, make cylindrical lithium ion secondary battery according to the method identical with comparing embodiment 1.
Specifically, by using double arm kneading mixer to stir the acrylic-nitrile rubber (solid constituent of the BM-720H (trade (brand) name) that produces by ZEONCorporation) of 490g solid electrolyte particle, 480g inorganic oxide filler, 30g modification and the NMP of appropriate amount, prepare paste.Except this paste being administered on the both sides of negative pole ring, then dry, to form in every side outside the thick solid electrolyte layer of 5 μ m, implement and comparing embodiment 1 identical operations.
Embodiment 4-8
Except the thickness of every side solid electrolyte layer being changed into 5 μ m (embodiment 4), 10 μ m (embodiment 5), 15 μ m (embodiment 6), 25 μ m (embodiment 7) and 30 μ m (embodiment 8), on the both sides of negative pole ring, form solid electrolyte layer according to the method identical with embodiment 3.In addition, except using this negative pole ring, and do not use outside the barrier film, make cylindrical lithium ion secondary battery according to the method identical with comparing embodiment 1.
Embodiment 9
Except using average grain diameter is that the titanium dioxide of 0.3 μ m replaces Alpha-alumina as the inorganic oxide filler, makes cylindrical lithium ion secondary battery according to the method identical with embodiment 4.
Embodiment 10
Except using average grain diameter is that the zirconia of 0.3 μ m replaces Alpha-alumina as the inorganic oxide filler, makes cylindrical lithium ion secondary battery according to the method identical with embodiment 4.
Embodiment 11
Except using average grain diameter is that the magnesium oxide of 0.3 μ m replaces Alpha-alumina as the inorganic oxide filler, makes cylindrical lithium ion secondary battery according to the method identical with embodiment 4.
Should be understood that when the major axis of solid electrolyte particle in embodiment 1-11 is set to less than 0.1 μ m difficulty is used the paste that comprises solid electrolyte particle and binding agent equably, and has reduced productivity ratio.In addition, for the battery that the solid electrolyte particle that uses major axis less than 0.1 μ m obtains, need the long period with nonaqueous electrolyte impregnated electrode group.On the other hand, when the major axis of solid electrolyte particle changes over 4 μ m, the situation in big space occurs producing, formation dendrite may be induced in these big spaces in solid electrolyte layer.
When in embodiment 1-11, the thickness of solid electrolyte layer being changed over 3 μ m, in some batteries, confirm to produce leakage current.Therefore, find preferably the thickness of solid electrolyte layer to be arranged to be not less than 3 μ m.In addition, when the thickness of solid electrolyte layer during greater than 30 μ m, the pliability of solid electrolyte layer reduces, and observes the reduction of productivity ratio and the increase of the internal resistance of cell.Therefore, find preferably the thickness of solid electrolyte layer to be arranged to be no more than 30 μ m.
Embodiment 12
Except on the thick solid electrolyte laminar surface of 5 μ m, forming the polyolefin layer, make cylindrical lithium ion secondary battery according to the method identical with embodiment 4.
Specifically, by using double arm kneading mixer to stir the NMP of 980g, prepare paste as acrylic-nitrile rubber of the high purity polyethylene particle of polyolefin particles (fusing point is that 133 ℃ and average grain diameter are 1 μ m), 20g modification (solid constituent of the BM-720H (trade (brand) name) that produces by ZEON Corporation) and appropriate amount.Except this paste is administered on the solid electrolyte laminar surface, then dry, to form in every side outside the thick polyolefin layer of 5 μ m, implement and embodiment 4 identical operations.
Embodiment 13
Except arrangement conversely, make cylindrical lithium ion secondary battery according to the method identical with embodiment 12 with solid electrolyte layer and polyolefin layer.
Specifically, except at first on the both sides of negative pole ring, using the paste that comprises polyolefin particles and binding agent, then dry, to form the thick polyolefin layer of 5 μ m in every side, on the surface of polyolefin layer (PO layer), use the paste that comprises solid electrolyte particle, inorganic oxide filler and binding agent then, then dry, to form the thick solid electrolyte layer of 5 μ m in every side.
Embodiment 14
The paste that will comprise the preparation in embodiment 12 of polyolefin particles and binding agent is administered on the both sides of negative pole ring, and is then dry, to form the thick polyolefin layer of 5 μ m in every side.On the other hand, will comprise that the paste of the preparation in embodiment 3 of solid electrolyte particle, inorganic oxide filler and binding agent is administered on the both sides of anode ring, then dry, to form the thick solid electrolyte layer of 5 μ m in every side.Except the anode ring that uses acquisition like this and negative pole ring and do not use the barrier film, make cylindrical lithium ion secondary battery according to the method identical with comparing embodiment 1.
Embodiment 15
The paste that will comprise the preparation in embodiment 3 of solid electrolyte particle, inorganic oxide filler and binding agent is administered on the both sides of anode ring, and is then dry, to form the thick solid electrolyte layer of 5 μ m in every side.Then, will comprise that the paste of the preparation in embodiment 12 of polyolefin particles and binding agent is administered on the surface of solid electrolyte layer, then dry, to form the thick polyolefin layer of 5 μ m in every side.Except the anode ring that uses acquisition like this and do not use the barrier film, make cylindrical lithium ion secondary battery according to the method identical with comparing embodiment 1.
Embodiment 16
The paste that will comprise the preparation in embodiment 3 of solid electrolyte particle, inorganic oxide filler and binding agent is administered on the polytetrafluoroethylene (PTFE) sheet, and is then dry, and when itself and PTFE sheet are separated, obtains the thick solid electrolyte sheet of 25 μ m.Except between anode ring and negative pole ring, inserting this solid electrolyte sheet and do not use the barrier film, make cylindrical lithium ion secondary battery according to the method identical with comparing embodiment 1.
Embodiment 17
The paste that will comprise the preparation in embodiment 3 of solid electrolyte particle, inorganic oxide filler and binding agent is administered on the polytetrafluoroethylene (PTFE) sheet, and is then dry, to form the thick solid electrolyte layer of 5 μ m on the PTFE sheet.Then, will comprise that the paste of the preparation in embodiment 12 of polyolefin particles and binding agent is administered on the surface of this solid electrolyte layer, then dry, to form the thick polyolefin layer of 5 μ m.When this is two-layer and PTFE sheet are separated, obtain the thick solid electrolyte sheet of 10 μ m.Except between anode ring and negative pole ring, inserting this solid electrolyte sheet and do not use the barrier film, make cylindrical lithium ion secondary battery according to the method identical with comparing embodiment 1.
Embodiment 18
The acrylic-nitrile rubber that replaces modification except the mixture of polystyrene (PS) resin of weight such as use and poly(ethylene oxide) (PEO) is as the binding agent in the solid electrolyte layer, makes cylindrical lithium ion secondary battery according to the method identical with embodiment 2.
[evaluation]
Estimate the battery of embodiment and comparing embodiment by following method.
The situation of solid electrolyte layer
By visual examination whether any chip, crackle or separation taking place in solid electrolyte layer, observes the situation of every layer of solid electrolyte layer of firm formation.In all embodiments, the situation of solid electrolyte layer is good.
The electrode outward appearance
By visual examination whether for example any problem of size change taking place, observes the situation of the negative or positive electrode after solid electrolyte layer has just formed.In all embodiments, the electrode outward appearance is good.
The pliability of solid electrolyte layer
Twine positive pole and negative pole around core, be inserted with solid electrolyte layer therebetween, thereby form 10 semi-finished product electrode groups for each embodiment.Then, take winding apart, and whether any chip, crackle or separation take place in solid electrolyte layer, mainly the situation by near the part solid electrolyte layer visual observation core by visual examination.Only in the battery of embodiment 8, defective occurs, in all the other embodiment, do not observe defective.
The design of battery capacity
Although the internal diameter of battery can be 18mm, the diameter of electrode group is set to 16.5mm before insertion.Anodal weight obtains the design capacity of each battery from this design, and the capacity of getting every gram positive electrode active materials is 142mAh.The result is illustrated in the table 1.
Charge
With flawless, complete battery pre-charge/discharge twice, and under 45 ℃ environment, laid in 7 days.Then, as described belowly in 20 ℃ environment charge and discharge:
(1) constant-current discharge: 400mA (final voltage 3V)
(2) constant current charge: 1400mA (final voltage 4.2V)
(3) constant voltage charge: 4.2V (stopping electric current 100mA)
(4) constant-current discharge: 400mA or 1400mA (final voltage 3V)
The charging of this moment is illustrated in the table 1.
The fail safe that nail is penetrated
Make each battery after charge is estimated in 20 ℃ environment, accept charging as described below:
(1) constant current charge: 1400mA (final voltage 4.25V)
(2) constant voltage charge: 4.25V (stopping electric current 100mA)
In 20 ℃ environment, the iron wire nail of the 2.7mm diameter speed with 5mm/sec or 180mm/sec is penetrated the battery of each charging from its side, and the heat of observation battery this moment produces state.The temperature of having represented battery when nail penetrates 1 second of back and 90 seconds in the table 1.
Should be understood that the result who penetrates when as nail, when positive pole contacts (short circuit) with negative pole, produce Joule heat.The barrier film that thermal endurance is low is melted by Joule heat, and forms firm short circuit part.Therefore, continue to produce Joule heat, and temperature increases to positive pole and becomes heat-labile zone.When reducing the nail penetration speed, local heat production is quickened.Reason is to have limited the short circuit area that time per unit produces, and has concentrated a large amount of heat in limited position.On the other hand, when increasing the nail penetration speed with the short circuit area that enlarges time per unit and produce, heat dissipates in big zone, thereby the temperature of having slowed down battery increases.
Table 1
PO layer: polyolefin layer; The AN of modification: the acrylic-nitrile rubber of modification;
PS: polystyrene; PEO: poly(ethylene oxide); SE layer: solid electrolyte layer
Table 1 (continuing)
Hereinafter, evaluation result is described.
(i) about there being or not existing solid electrolyte layer
In the comparing embodiment 1 that does not have solid electrolyte layer, no matter the nail penetration speed how, nail obviously is overheated after penetrating for 1 second.On the contrary, on electrode surface, among the embodiment of bonding solid electrolyte layer, significantly suppressed overheated after nail penetrates.Take and check each battery behind the nail penetration test apart, large-area barrier film is melted in the battery of comparing embodiment 1.On the other hand, in each embodiment, solid electrolyte layer keeps its original state.This shows that when solid electrolyte layer has sufficient thermal endurance even cause internal short-circuit and battery generation heat because nail penetrates, solid electrolyte layer will can not damage yet.Therefore, it seems use solid electrolyte layer can suppress the expansion of short-circuited region and prevent overheated significantly.
(ii) about the thickness of solid electrolyte layer
As if although resistance increases along with the increase of solid electrolyte layer thickness, battery behavior is smaller to the dependence of solid electrolyte layer thickness, as shown in embodiment 4-8.This shows that solid electrolyte layer is little for the influence of internal resistance.But, when the amount of the binding agent that comprises in the solid electrolyte layer was very big, the trend that internal resistance increase and battery performance reduce appearred.On the contrary, when the amount of the binding agent that comprises in the solid electrolyte layer was minimum, the intensity that solid electrolyte layer occurs reduced and damages the situation of solid electrolyte layer when making up the electrode group.
(iii) about the type of binding agent
In modified propylene nitrile rubber (rubber-like polymer that comprises acrylonitrile unit) each embodiment that uses appropriate amount, make up the electrode group easily, and battery behavior is good as binding agent.Should be understood that among the embodiment 18 that the polystyrene (PS) that uses and poly(ethylene oxide) (PEO) seem has experienced oxidation under 4V or higher voltage, although they have excellent flexibility.
(iv) about the type of inorganic oxide filler
The user of inorganic oxide filler with liquid electrolyte impregnated electrode group, thereby make and can shorten operating time in the battery manufacture process.In using aluminium oxide, titanium dioxide, zirconia and magnesian any situation, similarly obtain this effect basically.For example, when relatively using required time of liquid electrolyte impregnated electrode group between embodiment 7 and embodiment 2, the time that embodiment 7 needs is 1/4th of time of needing of embodiment 2.
(v) as for the bonding position of solid electrolyte layer
When changing the bonding position of solid electrolyte layer, also can realize similar charge and the fail safe that nail is penetrated.But so that polyolefin layer when contacting with positive pole, the life characteristic of battery has the trend of slight reduction when form solid electrolyte layer on negative terminal surface.In addition, shown in embodiment 16-17, when not boning with electrode surface, also can realize solid electrolyte layer the favourable fail safe that nail is penetrated.The reason seemingly key component of solid electrolyte layer is solid electrolyte or inorganic filler, and therefore, thermal contraction does not take place in most applications solid electrolyte layer.Yet from production operation time or the consideration of productive rate angle, preferably the surface with solid electrolyte layer and electrode bonds.
(vi) about polyolefin layer
For each battery that comprises polyolefin layer, in the nail penetration test, obtain particularly advantageous result.Effect has been brought into play in the choked flow (closing function) of seemingly poly heat-absorbing action of reason and melting polyethylene.When using polypropylene to replace polyethylene, also improved fail safe.
Preparations and above-mentioned similar battery such as the composition by changing electrode material within the scope of the invention, solid electrolyte layer, polyolefin layer, and, find that each battery all is being excellent aspect charge and the fail safe by evaluation.
In addition, except using LiTi respectively
2(PO
4)
3-AlPO
4, LiI-Li
2S-SiS
4, LiI-Li
2S-B
2S
3, LiI-Li
2S-P
2O
5And Li
3N replaces LiCl-Li
2O-P
2O
5Be used for outside the solid electrolyte particle, make cylindrical lithium ion secondary battery according to the method identical with embodiment 1,4,12 etc., and by with identical as mentioned above evaluation, find that each battery realized the identical effect with embodiment 1,4,12 etc.
Industrial applicability
The present invention is particularly useful for providing and has excellent security and the height of charge/discharge characteristics The performance lithium rechargeable battery. Lithium rechargeable battery of the present invention is high safety, therefore Be particularly suited for the power supply as portable set.
Claims (15)
1. lithium rechargeable battery, it comprises:
The positive pole that comprises lithium composite xoide; Can charge into and discharge the negative pole of lithium ion; Non-aqueous electrolyte; And be inserted in solid electrolyte layer between described positive pole and the described negative pole,
Wherein said solid electrolyte layer comprises solid electrolyte particle and binding agent.
2. the lithium rechargeable battery of claim 1, wherein said solid electrolyte layer comprises the inorganic oxide filler.
3. the lithium rechargeable battery of claim 1, bonding one of at least in the surface of wherein said solid electrolyte layer and described positive pole and the surface of described negative pole.
4. the lithium rechargeable battery of claim 1, wherein said solid electrolyte particle comprise and are selected from LiCl-Li
2O-P
2O
5, LiTi
2(PO
4)
3-AlPO
4, LiI-Li
2S-SiS
4, LiI-Li
2S-B
2S
3, LiI-Li
2S-P
2O
5And Li
3At least a among the N.
5. the lithium rechargeable battery of claim 2, wherein said inorganic oxide filler comprise and are selected from least a in titanium oxide, zirconia, aluminium oxide and the magnesium oxide.
6. the lithium rechargeable battery of claim 1, wherein said binding agent comprises the rubber-like polymer that comprises acrylonitrile unit at least.
7. the lithium rechargeable battery of claim 1, wherein said solid electrolyte particle has the flakey shape.
8. the lithium rechargeable battery of claim 7, the major axis of wherein said solid electrolyte particle is not less than 0.1 μ m and is not more than 3 μ m.
9. the lithium rechargeable battery of claim 1, wherein said solid electrolyte layer has the thickness that is not less than 3 μ m and is no more than 30 μ m.
10. the lithium rechargeable battery of claim 1 wherein further insert polyolefin layer between described positive pole and described negative pole, and described polyolefin layer comprises polyolefin particles.
11. the lithium rechargeable battery of claim 10, wherein bonding one of at least in the surface of the surface of described polyolefin layer and described positive pole and described negative pole.
12. the lithium rechargeable battery of claim 10, wherein said solid electrolyte layer is bonded to the surface of described negative pole, and described polyolefin layer is bonded to the surface of described solid electrolyte layer.
13. the lithium rechargeable battery of claim 10, wherein said polyolefin layer is bonded to the surface of described negative pole, and described solid electrolyte layer is bonded to the surface of described polyolefin layer.
14. the lithium rechargeable battery of claim 10, wherein said polyolefin layer is bonded to the surface of described negative pole, and described solid electrolyte layer is bonded to the surface of described positive pole.
15. the lithium rechargeable battery of claim 10, wherein said solid electrolyte layer is bonded to the surface of described positive pole, and described polyolefin layer is bonded to the surface of described solid electrolyte layer.
Applications Claiming Priority (3)
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|---|---|---|---|
| JP144503/2004 | 2004-05-14 | ||
| JP2004144503 | 2004-05-14 | ||
| JP328747/2004 | 2004-11-12 |
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| CN107408700A (en) * | 2015-03-18 | 2017-11-28 | 日立化成株式会社 | Adhesive resin composition, electrode for lithium ion secondary battery and lithium rechargeable battery |
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| JP4478706B2 (en) * | 2007-09-05 | 2010-06-09 | セイコーエプソン株式会社 | Lithium ion conductive solid electrolyte and all solid lithium secondary battery using the same |
| JP5277859B2 (en) * | 2007-12-03 | 2013-08-28 | セイコーエプソン株式会社 | Sulfide-based lithium ion conductive solid electrolyte glass and all-solid lithium secondary battery |
| CN101841060A (en) * | 2010-05-20 | 2010-09-22 | 复旦大学 | Lithium ion battery using lithium manganate as anode material |
| JP5182977B1 (en) * | 2012-02-24 | 2013-04-17 | 株式会社日立製作所 | Lithium ion secondary battery electrode and lithium ion secondary battery |
| JP6390101B2 (en) * | 2013-03-18 | 2018-09-19 | Tdk株式会社 | Solid lithium ion conductor and electrochemical device |
| WO2016129428A1 (en) * | 2015-02-12 | 2016-08-18 | 富士フイルム株式会社 | All-solid secondary battery, solid electrolyte composition and electrode sheet for battery used therein, and methods of manufacturing electrode sheet for battery and all-solid secondary battery |
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| CN107645013A (en) * | 2016-07-22 | 2018-01-30 | 中国科学院物理研究所 | Compound quasi-solid electrolyte, its preparation method and the lithium battery or lithium ion battery containing it |
| JP6640690B2 (en) * | 2016-09-21 | 2020-02-05 | 株式会社東芝 | Electrode structure, secondary battery, battery pack and vehicle |
| CN108376783B (en) * | 2018-02-09 | 2020-10-23 | 四川华昆能源有限责任公司 | Lithium anode surface protective coating and preparation method thereof |
| JP6889125B2 (en) * | 2018-03-16 | 2021-06-18 | 株式会社東芝 | Separator, electrode group, secondary battery, battery pack, vehicle, and stationary power supply |
| CN108962613B (en) * | 2018-06-11 | 2020-08-11 | 中国科学院电工研究所 | Method for reducing leakage current of lithium ion capacitor |
| CN109449492B (en) * | 2018-11-01 | 2022-03-29 | 中南大学 | Ceramic-based all-solid-state battery and preparation method thereof |
| EP3940818B1 (en) * | 2019-03-12 | 2023-12-06 | Mitsubishi Gas Chemical Company, Inc. | Method for producing all-solid-state battery |
| CN113394463A (en) * | 2021-04-25 | 2021-09-14 | 浙江锋锂新能源科技有限公司 | Sulfide-based solid electrolyte all-solid-state battery and preparation method thereof |
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