2) United States Patent Zhang et ($4) LITHIUM ION BATTERY USIN CROSSLINKABLE SEPARATOR (71) Applicant: Asahi Kasel Kubushiki Kalsha, Tokyo ) (72) Inventors: Xun Zhang, Tokyo (IP); Ryo Kuroki Tokyo (IP), Vuki Fukunaga, Tokyo (IP); Hiromi Kobayashi, Tokyo (IP), Mitsuko Saito, Tokyo (JP) (73) Assignee: Asahi Kasel Kabushiki Kala, Tokyo ) (4) Notice: Suijct to any disclaimer, the tem of this patent is extended of adjusted under 35 USC. 154(b) by 199 days (21) Appl. Now 160987,421 (22) PCT Filed: Oct. 11,2019 (85) PCT'No: — PET/SP2019/040343 § 371 (XI), (2) Dawe: Jum, 24, 2020 (87) PCT Pub. Nos WO20200075866 PCT Pub. Date: Apr: 16, 2020, ws) Prior Publication Data S 202010335755. A Oct. 22, 2020 G0) Foreign Application Priority Data et. 1, 2018 GP) Ip2018-192975 et 11, 2018 UP) 120186192978 (Continued) (51) Inte noi 2 (2006.01) HOLM Su4se (2021.01) (Continued) i | T 2 | | 3 | | oane t t 3] 1 :| |_| | | | a | i f =e Atter crsslinkine | ——Reference membrane ae 0 2 0% 0 1 Temperature: too T Transitjon. | temperature | USO! 1588208B2 (10) Patent No.: (4s) Date of Patent: US 11,588,208 B2 Feb. 21, 2023 (62) US.CL coc HOIM swt (2021.01); COBS 2724 (2013.01); HOLM 100568 (2013.01); HOIM ‘30/403 (2021.01) (58) Fleld of Classification Search cre HOIM 4102 ‘See application fie for complete search history 60) References Cited US. PATENT DOCUMENTS $998,065 1211999 Teutsumi a 2006009378 81 '5/2006 Ohashi ea (Continved) POREIGN PATENT DOCUMENTS ow IDS7IL A 22006 &N wolsosies A 122009 (Continved) (OTHER PUBLICATIONS Inverasional Peiminary Report on Patent and Writen Opin fon issued in corespending Intemational Patem Application No. PCTIP2O19/04034% dated Ape. 8, 2071 (Continaed) Primary Examiner — acolo B Macks (74) Attornes, Agent, or Firm — Morgan, Lewis & Bockius LLP 6 ABSTRACT A separator for aa eletricity storage device comprising 3 silane-modifed polyolefin, wherein silane erosslinkingrene- tion of the silane-modified polyolefin is initiated when it contacts with the electrolyte solutions well asa method for producing the separator. 22 Claims, 10 Drawing Sheets Rubber piateau epee eee KS 125 tooUS 11,588,208 B2 ase? 30 oretgn Applicaton Priority Data mm —aaonns a oe ace - 2 2012076370 A Now. 1, 2018 (P) sp2ois-2n6048 2 2012821618 Ape 23,2019 GP) ‘p2019-082088 3 2o3.anke0 A M31 2019. GP) Booisiaian um iat, 2019 OP) moots kaw A ” a sy) teen ” 5 Coss 324 (2006.01) Bir oboe & HaIM 1aases (2010001) A anes fois Sauer’ hat 01) Hi ie He aah oes & $6) References Cited Et foanttaoremo & Ei tessa A USS. PATENT DOCUMENTS Rt foanisoryse & Rt tanleotaeiss A 2ooroisto AL $2007 teiawa eal Et inant & Joogortsey al Som Cale Et foa0rtou & Soveliere Al 93m Kamas ea Ke tnan17 10120 A Soventees Al 16200 Mane". nouioose KR tants.azies A woth onal Bs Sotneeaes At 3010 Raa a Wo alaisasss AL aLao.0 Bilvorsste At G01 Panam se we ‘oh 20110232836 9/2011 Uetani et al. 10 122014 DOWOSLINTS AL 122011 naga ea Wo do1siiT6ss0 AL 112018 Sozeuie at ‘e202 Site Sa Soames At S018 lag ca omni punticarions Sorgoree AI Sault fens ae eee ‘Supplementary European Search Report issued in corresponding oieolzsie At $2016 Pak ta Faropan Patt Aplin No~ 96776 aed No.8 2021 Pere Ne eee Tone Cn “Prclom oy Steen Bares nel iene tania [en Sumlay Hat Gnd any p 3850 Mr 2,09) Gs oiooot At ‘Lanso Akea tera neh tan Stanweroea AL 2aoz0 Rim sal Sino ten "salon hom” Kin Kot a PORFIGN PATENT DOCUMENTS ow oaeswons a. ow oxns209 A. aw Toasissre a. rou Tos10ass0 A. ow Tostastea A ow Tosiowose DE 102012000910 AL BP 3862767 AL dongtet AL 3aon AL ATI9061 AL ° So 78005 A. » HoD-s16961 ® mlo-261433 A, iP HUIcLdTa9 » HUIcL2036 ® 2000319441 A iP 2001-6484 A ® Sox A ® 2005008813 A ie doveanaesk A ® douect 0209 A » Joorae6i2 A ® ‘0.070620 A oIL-D0s60 A Laois 9203 42018 112016 12017 e208 Tos 208. Sonis 62018, 02020 31989 Sim7 9 1998 51099 G19 112000 ‘62001 S003 12005 4006 7006 00? 4009 1201 ‘The Society of Polymer Science, p. 173 ul 1, 2006) (se patil English tanstatio). ‘Van de Wei, ~The Action of Tin Compounds in Condensation-ype RIV Silicone Robbers,” Macromolecular Chemisty Physics, ISI, 2541-2548 (1980), Iteration Search Report issue in covrespondiag latermatinsl Patent Application No. PCTIP2019 0403) dated lan. 7, 2020. Soplementary European Search Repo issued in corresponding Enopean Patent Application No, [ISTULIG dated Nov. 29.2031 ‘Koyama, "Measurement of Physical Propertis of Polymeric Mate rials under High Pressure," Thereviw of high presse sience and technology $4 204-251 Sep. 30, 1996 (ace English asta). arial Furopean Search Repor issued in related Buropea Patent Application No, 22160052.2 dated Aug. 4 2022 artal Euopean Search Report issued inwlated European Patent Application No. 22169036 dated Avg. 16,2022. "Extended Ewropean Search Repo issue lated European Patent ‘Application No. 2216002000 dated Aug. 18, 2022 "Exended Europea Search Rept issued late European Patent Application NO. 221690423 dated Au. 8, 2022, "Extended Eropean Search Repo issue lated European Patent Aprliation No. 221690365 dated Oxt 27,2022, "Exended ropeaa Search Iept issued late European Patent ‘priiation No. 221690822 dated Oxt 27,2022, * cited by examinerU.S. Patent Feb. 21, 2023 Sheet 1 of 10 US 11,588,208 B2 FIG.1 Monbrane rupture Rubber plateau Storage modulus E'(Pa) | Transition | temperature > === After crosslinking —} Reference menbrane | aaeee eacaneesasaae Pee ee er Temperature (°C) Membrane rupture Loss modulus E”(Pa) ~~~ After cross! inking —— Reference membrane 50 -25 0 2 50 75 «6100 125 150 175 200 225 Temperature (°C)U.S. Patent Feb. 21, 2023 Sheet 2 of 10 US 11,588,208 B2 FIG.3 E+06 5 1.E+05 1. E+04 E+03 Resistance (2) 1. £402 ~ 1. £+01 be eee ee Dee ees eee E+00 35 «50 Temperature (°C)U.S. Patent Feb. 21, 2023 Sheet 3 of 10 US 11,588,208 B2 FIG. 4 Example 1 10000 = 1000 & 8 torage modulus /MPa 7 ' oss modulus /MPa — Gap distance mm 0. — 20 ~50 0 50 «100150 200 250 300 Temperature/°C (b) Comparative Example 1 10000 r 20 n 18 & | 5 = 5 tio = a2 fos 3 | @ 8 |, = oe +o g Bs Storage modulus /MPa | i oss modulus /MPa . 5 — Gap distance mm 1 | 0.1 * * * ro " + 10 ~50 0 50 100 150 200 250 300 Tenperature/*CU.S. Patent First derivative of gap displacement d mm/d°C First derivative of gap displacement d mm/d°C 0, 25 -0.3 Feb. 21,2023 Sheet 4 of 10 FIG.5 Example 1 Temperature/*C 50 0 50 100 150 200 250 300 4 20 nN en ee, 1a 5 r | _ Softening a — transition L/” temperature —— First derivative 5 of displacement — Gap distance 0 “5 Comparative Example 1 Temperature/*C ~50 0 50 100 «150 =. 200-250 300 — — First derivative of displacement 15 —— Gap distance Softening 10 transition ‘temperature 5 0 “5 US 11,588,208 B2 Gap distance /nm Gap distance /mmU.S. Patent Feb. 21, 2023 Sheet 5 of 10 US 11,588,208 B2 Crystal portion ‘Amorphous vrs] alee ~ interlayer portion FIG.7 Crystal growthU.S. Patent Feb. 21, 2023 Sheet 6 of 10 US 11,588,208 B2 FIG.8 Change in orystal structure in tensile rupture fracture test 100% 80% 60% ——>— After chemical 40% cross! inking —— Before chemicai 20% > cross! inking Crystal fragmentation rate seeeees EB cross! inkingU.S. Patent Feb. 21, 2023 Sheet 7 of 10 US 11,588,208 B2 FIG. 9 | \ Membrane rupture T Rubber pl lL] 2 teau | | Transition temperature ~ == After cross! inking ‘" [a Reference membrane ture temperature. PTL 1, for example, deseribes adjustanent ‘of the higher physical properies of a polyolefin resin as an ‘essential component of separator for a lithium ion battery In addition, as deseribed in PTL 2, i is known that heat release due to interior battery shot circuiting is inhibited by ‘shutdown function when the degree of erystallinity and gel {faction are in spevitic ranges, and that the safety ofa battery ‘can be ensured i it has performance such that » membrane rupture does not oceur in the battery cell at partial high temperature sections (i.e. breakdown at 170° C. or higher). More specifically, in regard to PTL | and 2, i has gradually ‘come 10 light by experimentation that high-temperature membrane rupture properties can be exhibited by constrct- ing silane crosslinked sections (a gel structure) in a poly- ‘olefin separator. PILs 1 to 6, for example, describe a silane crosslinking structure formed by eontaet hetween asiane-mdifed poly= olefin-containing separator and water PIL 8 describes 3 ‘rosslinke! structure formed Irom ring-opening of norbor- rane by ieadation with ultraviolet rays or an elecieon bea. PTL. 9 deseribesa separator insulating layer having a (meth) ‘acrylic acid eopolymer with a crosslinked structure, and a syrene-butadiene rubber binder. A separator has also been proposed that has layer A having a shutdown property and a layer B comprising an aramid resin and an inorganic material, with the mitio of their thicknesses adjusted to within a preseibed range (soe PTL 11) "The members used in lithium ion battery area positive ‘electrode, a negative electrode material, an electrolyte oh tion and a separator. Among these members, the separator must be inactive from the standpoint of electrochemical reaction and with respect othe peripheral members, Because ff its role as an insulating material. Since development of the first negative electrode materials for lithium ion batter jes, a method has been established for inhibiting decompo- sition of the electrolyte solution on the negative elecrode surface, wherein a solid electrolyte interface (SEI) is Formed by chemical reaction during inital charge (NPL. 1). Even ‘shen a polyolefin esi is used asthe separator, some cases have been reported in which oxidation reaction is induced on the positive electmde surface at high voltage, resulting ia blackening or surface degradation of the separator 2 For this reason, the materials used for electicity storage device separators are designed with chemical structures that fare inert in electrochemical reactions of other chemical reactions, ad as a result, polyolefin microporous mem- branes have become widely developed and implemented. When polyolefin is used as the resin, however, the ‘improvement in performance has been limited even when the mechanical mieropore structure of the separator is mod fied. For example, when the performane is insullcient in terms of the heat-resistant stability of the separator at above the melting point of the polyolefin, or in terms ofthe ainity with the electrolyte solution oF the Tiguid retention due to clectronegativity of the olefin wits, i is not possible to ‘oblain satisfactory permeability of Li ions or their solvated fon clusters in the separator. ‘Because of such limitations, therefore, by curreat mea it is not possible to satisfy the high-speed charge-dischange fr heat stability required for modem battery development CITATION LIST Patent Literature {PTL 1] Japanese Unexamined Patent Publication No, H09 (1997)-216964 {PTL 2} International Patent Publication No. WO97/44839 [PTL 3} Japanese Unexamined Patent Publication No. HLL (1999) 144700 [PTL 4} Japanese Unexamined Patent Publication No. HL (1999)-172036 PTL 5] Japanese Unexamined Patent Publication No, 2001- 176484 {[PTL.6] Jgpanese Unexamined Patent Publication No. 2000- 319441 [PTL7] Jgpanese Unexamined Patent Publication No. 2017- 203145 [PTL8] Japanese Unexanined Patent Publication No. 2011- o738 [PTL 9] Japanese Unexamined Patent Publication No, 2014- 056883 [PTL 10] Japanese Unexamined Patent Publication No, H10(1998)-261435 IPTL 11] Japanese Unexamined Patent Publication No. 2007-299612 {PTL 12] International Patent Publication No. WO2010/ 134585 [PTL 13] Japanese Unexamined Patent Publication No, 2016072150 [Non Patent Literature INPL 1] Lithium ton Secondary Batteries (2nd Faition) ‘Nilkkan Kogyo Shimbun, Li INPL 2] Kiso Kobunshi Kagaku, Tokyo Kagaku Dojin SUMMARY, Technical Problem With dhe ineressing high outputs and high energy dens ‘ies of Tthiun ion secondary batteries for mobile devices and vehicles in recent years there is ongoing demand for smaller battery cell sizes and for stable cycle charge charge performance during long periods of use, Its there fore considered necessary for the separators used 10 be thin-membranes (for example, 15 ym or smaller) with high quality (for example, homogeneous physical properties andUS 11,588,208 B2 3 fee of resin aggregates). Standards have also become more rigorous for batery safety, and as also described in PTL 1 ‘and 2, there is @ need for shutdown functions and high: temperature membrane rupture properties, while expecta- tions are also high for development of separator resin ‘compositions that can be stably produced, and production methods for them. In this regard, the level for shutdown temperature is prefembly as far below 150° C. as possible, ‘while the mentbrane rupture temperature is preferably as high a temperature as possible In the method described in PTL 3, for example, a cross linking catalyst muster batch is used during the extrusion sep 10 promote silanesmodifed polyethylene erossinking reaction in he extruder, bu this resulisin generation of resin aggregates and lowers the homogeneity of the physical properties of the separator. Asa solution for this problen the methods described in PTLs 4 Sand 6 propose providing aplaticizer extraction step or silane gel crosslinking sep, oF ‘controlling the gel fraction of the resin membrane, of dewatering after casting of the uncroslinked resin through hot water. In addition, PTL 7 proposes a polyolefin micropo- rous membrane With modification of the gel fraction, the storage modulus at 40° C. to 250° C. based on dynamic viscoelasticity (DMA) measurement, the maximum shrink- age factor based on thermomechanical analysis (TMA) and ‘amount of radicals as measured by electron spin resonance (ESR), to provide a heat-resistant resin microporous mem- brane with low heat shrinkage, low Muidty and exeelfent meltdosin resistance. In addition, from the viewpoint of dimensional stability, sand of both maintaining the shutdown Function and incress- ing the membrane rupture temperature for separators for ‘electricity storage devices, it has been proposed to provide ‘an inorganic porous layer containing inomuanic particles such as calcined kaolin or bochmite and a resin binder oa at Teast one surlace of a polyolelin microporous membrane (PTs 12 and 13), However, the method disclosed in PTL 4 is notable 10 suficiently promote silane crosslinking reaction, and itis 14 {Chemis Formula 3} v3) ‘where X is hydrogen or a monovalent substituent, (Cem! Formula) ds ‘where X is hyeogen or a monovalent substituent, (Chemis! Formulas} CO: - where X is hyelgen or a monovalent substituent, and [Chon Forma) 0 where X is hyegen or a monovalent substituent Ba The separator for an electricity storage deviee secording 4 © [32] or [33] above, wherein: reaction (IV) is nucleophilic substitution reaction, ‘compound Ry bas a straight-chain unit yin addition to the linking reaction unit y,, and the straight-chain unit y, is one or more selected from the saroup consisting of divalent groups represented by the following formulas (yy-1) to (y.-6):US 11,588,208 B2 15 (Comical Foul or rn ‘where m isan integer of 0 t0 20, and n is an integer of 1 t0 20, (ee Forms AAS ‘where m is an integer of 1 t0 20, AN where is an integer of 1 40 20, ox (coil Foul 10) ~~ where is an integer of 1 40 20, ort) (Comical Formal ° ioe where X. ‘toms, alkylene or arylene group of 1 0 20 carbon id nis an integer of 110 20, and parry where X. ‘toms, an alkylene or arylene group of 1 0 20 carbon nis an integer of 1 10 20. 16 135) ‘The separator for an electricity storage deviee according {0 [32] above, where 5 the reaction (V) is meloophilie adition reaction, the funetional group x of compound Rx is one or more solectod from the group consisting of —OH, —NHs, NH, COOH and — SH, and the inking reaction wnit y, of compound Ry is one or ‘more selected from the group consisting of groups repre sented by the following formulas (Ay,-1) 16 (Ay,-6): = Ne ‘ Yr — of (CieicForm 15) avr s AN A [Chemist Formal 16) A, 4» where R is hydrogen oF @ monovalent organic group, {Ctemizl Formal 71 Ax « (een! Formula 8] % ay) en A (6) “The separator for an electricity storage deviee according {0 [32] above, where (6 the reaction (IV) is ring-opening reaction, the funetional group x of compound Rx is one or more selected from the group consisting of —OH, —NH, “NH, COOH and —SH, and 5 _ the linking reaetion unit y, of compound Ry consists of ‘wo oF more groups represented by the following formula (ROy,-1)US 11,588,208 B2 17 (Comal Formal 19) °. aye) x where the multiple X groups are each independently a hydrogen atom oF @ monovalent substitven i The separator for an elevtvity storage device according 'w [29] above, wherein in eation (V), the metal ion is one ‘or more selected from the group consisting of Zn", Ma Col, NP and Lit 8) Aseparitor for an electricity storage device comprising a fist porous layer (ayer A) that eludes a silane-moditied polyolefin and is capable of forming @ ersstinkedsteueture, and a second porous layer ayer B) that ineudesinoweanic pariles, wherein the heat shrinkage factor at 150° C. alee formation ofthe ersslinked structure is 0.02 w 0.91 times the heat shrinkage factor at 150° C. before formation ofthe crosslinked structure bo} “The separator for an electricity storage deviee acconting to [38] above, wherein the eroslinkd structure in ayer A js fomed by an acid, a base, swelling, or a compound enerated inside the electricity storage device. [o) ‘A separator for an electricity storage device, which com- prises ‘1 microporous membrane that includes a silane-modifed polyolefin and an inorganic porous Iyer tat inches inorganic particles and a resin binder, disposed on at least one surface of the microporous membrane. [at] ‘The separator for an electricity storage device aeconing 1 [40] above, wherein the content ofthe inorganic particles the inorganic porous layer is $ wt %6 0 99 wt [2} The separator for an electricity storage deve according 'e {40} of [41] above, wherein the content ofthe silanc- modified polyolefin in the microporous membrane is 0:5 wt 46 1 40 wi %. 18) ‘The separator for an electricity storage device aeconing to any one of [40] to [42] above, wherein the inorganic Pariles are one or more selected from the group consisting ‘of alumina (Al,0,) silica tania, zirconia, magnesia, cei, tri, zine oxide, iron oxide, silicon nite, titanium nitride, boron nitride, silicon earide, aluminum hydoxide oxide (AI|KCOH), ‘ae, keolnite, “dickte, naerte, halloysit, Pyrophyllite, montmorillonite, sericite, mica, amesite, ben. tonite, asbestos, zeolite, diatomaceous earth, guar sand and lass fibers (a) “The separator for an electricity storage deviee aecoring to any one of [40] t [43] above, wherein te glass transition temperature (Tg) of the resin binder is -50° C. to 100° C. 16s) “The separator for an electricity storage device aeconing to any one of [40] to [4], wherein silane crosslinking 0 o 18 action of the silane-modifed polyolefin is initiated when the scpartor for an electricity stonige device contacts with ‘an electrolyte solution, (46) ‘The separator for an electricity storage deviee according to any one of [40] to [45], wherein the separator for an electricity storage device fis ‘a stonige modulus change mtio (Ry) of 1S to 20-as efined by the following fomnula (1) where Bs the storage modulus measured at 160° C. 10 220° . forthe separator for an electricity storage device before crosiinking reaction of the slane-modified polyolefin, and Eryisthe storage modulus measured at 160° C. 0 220° C. for the separator for an electricity storage device aller exoss- linking reaction of the silane-modifid polyolefin, andor ‘loss modulus change ratio (Ra, af 1.5 4 20 a defined by the following formu (1B) where EY is the loss modulus measured at 160° C. to 220° (Cor the separator for an electricity storage device before crosiinking reaction of the silane-mosified polyolefin, and isthe loss modulus measured at 160° C. to 220° C. for the separator for an electricity storage device after exoss- Jinking reaction of the sitane-modifid polyolefin, ‘when measured afer the inoranie porous layer has been removed, wy, ‘The separator for an electricity stonige device according © any one of [40] to [46], wherein the separator for an clectricity storage device has ‘4 mixed storage moduls ratio (Reyes) OF 15 10 20-28 by the folowing formula (2) ‘where Fis the storage modulus measured at 160° C. 0 220° (Cfo the separator for an electricity stomige device and E', is the storage modus measured at 160° C. 10 220° C. for fa separator for an clctiity storage device aot containing the silane-modified polyolefin, and/or ‘aimed loss medulus aio (Ryyy,)of 1.5 to 205 defined by the following formula (2B) a , ow where E* is the loss modulus measured at 160° C,t0 2 C. for the separator Toran electricity storage device, and E is the loss modulus measured at 160° C. to 220° C. for as separator for an electricity storage device not containing the silane-modified polyolefin, when measured after the inor sganie porous layer las been removed [3] ‘The separator for an electricity storage deviee according to any one of [40] 10 [47] above, wherein, in the tempert- ture-dependent change ofthe storage modulas ofthe sepa- rior for an electricity storage deviee, the transition tem- perature of the rubber plateau and the crystal melt flow region is 138°C. t 150°C. (9) An clececity storie deviee comprising an electode, the separator for an electricity storage device according to any fone of [I] 10 [48] above, and a nonaqueous electrolyte solution 30), ‘An electricity stomge device comprising a sepamtor tht includes polyethylene, and an electrolyte solution or addUS 11,588,208 B2 five, wherein a functional group-modltied polyethylene o {unetional group graft copolymerized polyethylene meets with a chemical substine in the eletote solution oe acktve, forming a crosslinked struct (st) 'A mothod for prodcing the separator for an clectriity storage devi acconting to any ane of [I]t [$0] above, wherein the method! comprises the following steps: (1). shootforming sep in which a mixture of a silane- modified polyolefin, polsetilene anda. plastcier is ‘extra, cooled to solidification ad cast into-a shee ‘obtain a sheet (2) astrctching sep in which the shes is tothe atleast in a uniaxial cireton to obiin a steed sheet (6). porooshody-fomming step in which the plasticizer is ‘extacted fiom the stetched sheet in the presence of an ‘extacton solvent, forming pores in the suetche shoe 10 form a porous body and (4) a beat treatment step in which the porous body is subjected to eat weatment [52] ‘A method for producing « separator for an electricity storage device, which comprises the following sep: (a shet-forming step in which a ilne-modiisd poly ‘olein, polyethylene and plasticizer are ext into 9 sheet using an extruder, cooled to solidification and shaped into a molded sheet (2) 4 stetehing step in which the molded sheet is sub- Jocied to bianah stetching to a 20-fld to 250-fod area increase to form a steiches sheet (Gi) porous hody-forming step in which the plasticizer is ‘extracted from the sted sheet to form a porous body: (4) a hoot treatment step in which the porous body is suhjected to eat teatnent and subjected to stretching and relaxation in the transverse direction o obtain a heat-treated porous bods (GB) a outing step in which an inorganic porous layer including inorganic patcles and a resin binder formes on at east one surface of the heat-reated porous body to Forma a slase-crsslinking precursor and (0) asembly stp in which laminated stack or wound body of electrodes ant the silne-crosslinking precursor, and a nonagucos cectmste soliton, are hose in an exteroe body, contacting the silane-crossinking precursor wit the nonaqueous elective sation, 153] ‘An electricity storage device assembly kit comprising the following Wo elements: (an exterior hod housing a laminated stock or wound body of clectrdes and the separator for an clecrcty somagedeviee according to anyone of [1] 0 [48] above: and (@) acontainerowsng nonagunsscloctroytesoition. (54) The electricity storage device assembly kit according to [53] above, wherein the nonaqueous electrolyte solution ‘includes fvriae(F)-containiny ithe salt [53] “The electricity storage device assembly kit according 10 [53] or [54], wherein the nonagusous electrolyte solition includes lithium hexalluoopbosphate (Li). (56 “The electricity storage device assembly kit according to any one of [33] to [55], herein the nonaguccs elecisyte solution is an aed solttion andor a base solution. 0 o 20 57] A method for producing an electricity storage device ‘comprising the following steps ‘step of preparing the electricity stomge device assembly it according to any one of [53] to [56] above, and ‘step of contacting the separator for an electricity storage vice in clement (1) of the electricity storage device assembly Kit with the nonaqueous electrolyte solution in clement (2) t0 initiate silane crosslinking resetion of the silane- modified polyolefin 38) ‘The method for producing an electricity storage device according to [$7]. Which fuser comprises the following steps ‘a siep of connecting lead terminals to the electrodes of clement (1), and 8 stop of carrying out at least one eyele of charge discharge. 159), A method for producing an electricity storage device using a separator tbat includes a polyolefin, wherei: the polyolefin comprises one functional roup or two oF snore different fanetional groups, and the method for pro- ‘ducing an cletricty storage device comprises the following step: ‘a crosslinking step in which (1) condensation reaction is carried out between the functional soups 2) the funetional saroups are reacted with a chemical substance inside the electricity storage device, or (3) the functional groups are reacted with different types of functional groups, to form crosiinked stracture {60) ‘The method for producing an electricity storage device according to [59] above, wherein the crosslinking step is carried out ata temperature of 5° Ct 90° C, Advantageous Efets of Invention According to the invention itis possible to provide aa lecircity storage device which has a separator for an electricity storage device wih both alow temperature shut- ‘down fnction and high-lemperstare membrane raptire resistance, and inhibited generation of non-molten resin aggregates during the production process, thus contributing ‘0 productivity and economy, while also having satisfactory eyele characteristics and high salty, as well as an assembly it forthe san ‘Moreover, since itis not necessary to form the crosslinked structure during the membrane formation process or imme- lately afterwards forthe present invention, itis also pos- sible to inhibit inerease in internal stress ofthe separator oF its deformation immediately after fabrication of the elec- tricity storage device, and/or to impart erossinked strue- ture to the separator without using the relatively high eneray of photoiradiation or heating, and to thus reduce croslink- ‘unevenness, Furthermore, according othe invention itis Jet form a crosslinked streture not only within the eparator bi alo berwcen the separator and the eecrodes ‘and between the separator ad the slid electrolyte interface (GED, thus improving the strength between the different members ofthe electricity storage device, and also to reduce aps formed between te electrodes and the separator eased by their expansion/contraction during charge-dscharge of the electricity storage device, thereky notably improving ceyele stability daring prolonged useUS 11,588,208 B2 a BRIEF DESCRIPTION OF DRAWINGS FIG. 1 shows an example of «graph illustrating the relationship heween temperature and storage modus, con- teasing the storage modus of a reference membrane and a $ ‘rosslinked! membrane in temperature range of 50° C.t0 225" C,, and showing the transition temperature of the rubber plateau and erystal melt flow region. FIG. 2 shows an example of groph illustrating the relationship between temperature and loss moduls, con- teastng the loss modulus of a reference membrane and ‘crosslinked membrane in a temperature range of -50° C.t0 225" C., and showing the transition temperature of the rubber platews and crystal melt ow regi FIG. 3 is a groph showing the relationship between temperature and resistance for an electricity storage device ‘comprising the separator obtained in Example [1 TFG. 4 i a graph illustrating the relationship between the temperature, gap distance, storage modulus and loss mod- Jus in viscoelatiity measurement of a separator for an ‘lecricity storage device, with graph (a) for Example Hel fd grap (b) for Comparative Example I+ FIG. isa graph for detemining the membrane softening transition temperature in viscoelasticity measurement of & separator for an electricity sforage deviee, based on tem- perature, gop distance and fit derivative of gap displace- ‘ment, with graph (a) for Example H-1 and graph (b) for ‘Conyparative Example Tt FIG. 6 is @ schematic diagram illustrating a erystaline polymer with a higher-order structure, with the crystal 30 Structure divided into the lamella (crystal portion), the smomphous portion and te interlayer portion between them. FIG. 7 isa sehematic diagram illustrating crystal growth ‘ofa polyolefin molecule. IG, 8 isa stain-erysal fragmentation rate graph show: ing the change in X-ray erystal structure during a tensile ipture fracture test, for a membrane according 10 one nbowliment of the invent FIG. 9 shows an example of a graph illustrating the relationship between temperature and storage modulus, teasting the storage modulus ofa relerence membrane and & crosslinked! membrane in a temperature range of -50° C. 10 310° C,, and showing the transition temperature of the rubber plateau and crystal melt flow region. FIG. I shows an example of a grph illustrating the relationship between temperature and loss modulus, trostng the loss modulus of a reference membrane and & ‘rosslinked membrane in a temperature range of -50" C.t0 310° C., and showing the transition temperature of the rubber plateau and crystal melt flow region. FIG. 11s" H-NMR chart (a)and "C-NMR char (b) for silane-modified polyolefin starting material 1 obtained using 1 polyolefin FIG. 12 isa “HNMR chart (a) and °C-NMR eat (b) for silane-modified polyolefin staring material 2 obtained using «polyolefin FIG. 13 isa "H-NMR chart (a) and 'SC-NMR chart (b) for the separator obtained in Example I-, in the state before crosslinking, DESCRIPTION OF EMBODIMENTS 0 o Embodiments for carrying out the invention (hereunder refered to as “embodimonts") will now be explained in ‘dial. The present invention is not Himited tothe embod ments described below, and various modifications may be Implemented within the scope ofthe gist thereof. 2 Throughout the present specification, the “Wo” ina ‘numerical range means thatthe numerical values om either side are included as the upper limit and lower Timi. The ‘upper limits and lower Himits for the numerical ranges throughout the present specification may be combined as desired. For example, the upper limit ofa prefered numeri- cal ange may be combined with the lower limit ef'a more preferred numerical range, or conversely, the upper limit of ‘more preferred numerical ringe may’ be combined with the lower limit ofa prefered range ‘Throughout the present specification, “above”, “upper” ‘and “formed on the side” do not mean that the positional relationship of the respective members is “directly above”. Por example, the expressions “layer B formed on layer A" ‘and “layer B formed on the surfice of layer A" do. not exclude the ease where an arbitrary layer not qualifying as either is included benween layer A and ayer B. ‘The properties of the microporous membrane alone tht are described below may be measured after removing layers ther thant the microporoas membrane (for example, an ‘nonganic porous layer) fom the separator for an electricity storage device. ‘Separator for Electricity Storage Device ‘One aspect of the invention ie separator for an electricity storage device (hereunder aso refered (0 simply as “sepa- stor"). The separator, which must have an insulating prop- ery and ion permeability, will usually comprise an insult ing material sheet with a porous body structure, a polyolefin ‘nonwoven fabric or a resin microporous membrane. Parti larly suited fora lithium ion battery isa polyolefin micropo- ous membrane that allows constriction Of compact home- szencous porous body sinucture with redox degradation resistance ofthe separator. "A microporous membrane is a membrane composed of porous body, and its mean pore size is preferably 10:nm to ‘500 nm and more preferably 30 nm to 100 nm ‘When the separator is included in an electricity storage device, the separator ean be removed from the eleeeicity storage devie. Fit, Second, Thin, Fourth and Fifth Embodiments “The separator ofthe fist embodiment comprises a silane modified polyoleia, and optionally another polyolefin as well, When the separator of the first embodiment contacts with the electrolyte solution, silane crosslinking reaction of the silane-modified polyolefin in the separator is initiate. Since the separator of the first embodiment is able 10 crosslink the silane-modified polyolefin during eontaet with the electrolyte solution, it allows timing of crosslinking to be controlled so that crosslinking reaction can be carted out during the production provess for the eletrcity stone {ovce, instead of erosslinking reaction daring the separator production process. Tt isa feture ofthe separator of the second! embodiment that silane crosslinking reaction of the silane-modified poly- olefin takes place when it contacts with the electrolyte solution, According to the second embodiment, it is sul cient for silane crosslinking reaction to be observed during contact between the separator and electrolyte solution, regardless of whether of not the silane-modified polyolefin is present in the separator, or where the residual silane- ‘modified polyolefin fs, or whether the silane crosslinking reaction if fist initiated at contact with the electrolyte solution, oF whether it takes place sequentially oF conti ‘ously. The silane crosslinking reaction of the silane-modified