CN109921091A - A kind of composite material and preparation method and the lithium ion battery containing the composite material - Google Patents

A kind of composite material and preparation method and the lithium ion battery containing the composite material Download PDF

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CN109921091A
CN109921091A CN201910204685.4A CN201910204685A CN109921091A CN 109921091 A CN109921091 A CN 109921091A CN 201910204685 A CN201910204685 A CN 201910204685A CN 109921091 A CN109921091 A CN 109921091A
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composite material
nano
lithium
lithium ion
electrolyte
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CN109921091B (en
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唐伟超
李素丽
赵伟
袁号
李俊义
徐延铭
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Zhuhai Coslight Battery Co Ltd
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Zhuhai Coslight Battery Co Ltd
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Abstract

The present invention provides a kind of composite material and preparation method and the lithium ion battery containing the composite material, and the composite material includes sulfide electrolyte and nano-attapulgite stone, and the sulfide electrolyte coats nano-attapulgite stone.The present invention also provides the preparation method of above-mentioned composite material and contain the lithium ion battery of the composite material, the invention belongs to technical field of lithium ion, attapulgite after sulfide electrolyte cladding has club shaped structure and can form continuous vulcanization object electrolyte in nano-level leads lithium structure, make the cathode that there is good lithium ion transport performance, the lithium ion battery containing the composite material has a good application prospect.

Description

A kind of composite material and preparation method and the lithium ion battery containing the composite material
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of composite material and preparation method and contain this The lithium ion battery of composite material.
Background technique
Extensive use with lithium ion battery in fields such as electrical source of power, digital products, consumer is to lithium ion battery Security performance and energy density requirement it is higher and higher.There may be electrolyte leakages in use for liquid lithium ionic cell The safety issues such as liquid, kindling, explosion, meanwhile, the energy density of existing liquid lithium ionic cell becomes closer to theoretical limit, Technical bottleneck is increasingly prominent.Solid state battery has preferable safety and higher energy density, is that lithium ion battery develops Trend.
The mainstream route of current solid electrolyte is to use organic inorganic composite polymer electrolyte and sulfide electrolyte, How to realize that lithium ion is stable and quickly conducts inside solid state battery positive and negative electrode and in solid electrolyte phase, is promoted positive and negative The material property of pole and electrolyte, the overall performance for improving solid state battery, are the research emphasis of solid state battery.
For the performance for promoting all-solid-state battery, application No. is the Chinese invention patents of CN201610649224.4 to disclose one The method for kind preparing copper bismuth sulphur film, the plating metal bismuth on substrate, then vacuum evaporation CuS film again, then to coating on substrate It is handled, is prepared into copper bismuth sulphur film, the copper bismuth sulphur film of the invention mainly applies to semiconductor field, not to the material It is assessed in the application of field of lithium ion battery.Application No. is the Chinese invention patent applications of CN201810329907.0 to disclose The negative electrode material together of all-solid-state lithium-ion secondary battery, the cathode comprising it and all-solid-state lithium-ion with the cathode are secondary Battery, the negative electrode material together of the application for a patent for invention contain negative electrode active material, solid electrolyte and conductive material, negative electrode active material Matter includes selected from least one of metal and the oxide of the metal that can form alloy with Li, and solid electrolyte is sulfide Solid electrolyte, conductive material are conductive carbon material, but negative electrode active material also includes elementary silicon, in lithium ion battery charge and discharge In electric process, can there are problems that cathode is easy expansion and falls off.Major part sulfide electrolyte is in solid state battery application at present In mainly in the form of powder granule exist, currently also need continue fully optimized positive and negative anodes and electrolyte performance, to It is able to satisfy the requirement of industrialized production and application.
Summary of the invention
The first purpose of this invention is to provide a kind of composite material, and the composite material is sulfide electrolyte cladding Nano-attapulgite stone composite material, sulfide electrolyte cladding after nano-attapulgite stone nano-level have club shaped structure and Continuous vulcanization object electrolyte can be formed and lead lithium structure, there is good lithium ion transport performance.
A second object of the present invention is to provide a kind of preparation methods of composite material, pass through the parameter of ball milling burning process The selection of control and covering material controls coating thickness and coating layer material type, can improve sulfide in a certain range Electrolyte coats nano-attapulgite stone composite property, promotes the lithium ion transport performance and stability of composite material.
Third object of the present invention is to provide a kind of lithium ion battery, the lithium ion battery contains sulfide electrolyte Nano-attapulgite stone composite material is coated, sulfide electrolyte coats nano-attapulgite stone composite material in lithium ion battery It can effectively improve performance of lithium ion battery.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of composite material, the composite material include sulfide electrolyte and nano-attapulgite stone, the sulfide electrolyte Coat nano-attapulgite stone.
Further, thickness≤20um of the sulfide electrolyte clad, the nano-attapulgite stone stick crystalline substance are long 100nm-50um, wide 10nm-120nm.
Further, the sulfide electrolyte is one of following substance or a variety of combinations: aLi2S·b P2S5CLiX, wherein X represents halogens, 20≤a≤80,20≤b≤40,0≤c≤20;aLi2S·bP2S5CMeS, Middle Me is Si, Ge, Sn, Al or B, 20≤a≤80,20≤b≤40,0≤c≤20;aLi2S·bP2S5·cP2O5, wherein 67 < a < 80,0 < b < 40,0 < c < 25;Li4-aSi1-aPaS4, wherein 0 < a < 1;70Li2S·(30−a)P2S5·aP2S3, wherein 0 < a < 30;aLi2S·bSiS2, wherein 50≤a≤70,30≤b≤50;Li4-aSi1-aAlaS4, wherein 0 < a < 1;aLi2S· bSiS2·cLi3MO3, wherein M=B, Al, Ga or In, 20≤a≤80,20≤b≤40,0≤c≤20;aLi2S·bSiS2· cLi3N, wherein 20≤a≤80,20≤b≤40,0≤c≤20;aLi2S·bGeS2, wherein 0 < a < 60,40 < b < 100; 0.5Li2S·0.5[(1-a)GeS2·aGeO2], wherein 0 < a < 1;Li4+a (Ge1-aGab)S4, wherein 0 < a < 1,1 < b < 2;LiaGebPcS4, wherein 3≤a≤3.3,0≤b≤0.3,0.7≤c≤1.0;a(0.6Li2S·0.4SiS2)·bLi4SiO4, Wherein 80≤a≤100,0≤b≤20;LiaGebSecPdSe, wherein 3 < a < 4,0 < b < 1,0 < c < 2,0 < d < 1,2 < e < 4;LiaGebAscS4, wherein 3≤a≤3.5,0≤b≤0.5,0≤c≤0.5;LiaZnbGeS4, wherein 0 < a < 2,0 < b < 2;aLi2S·bP2S5·cGeS2·dSnSe2, wherein 20≤a≤80,20≤b≤40,0≤c≤10,0≤d≤10.
A kind of preparation method of above-mentioned composite material, comprising the following steps:
Step 1: based on molfraction, under ar gas environment, 40 ~ 100 parts of Li is weighed2S is dissolved in dehydrated alcohol, is added After 1.50 ~ 80.00 parts of nano-attapulgite stones are sufficiently impregnated bubble, under ar gas environment or room temperature vacuumize process, it is then heated to 50 ~ 90 DEG C, solvent absolute ethyl alcohol is removed, the nano-attapulgite stone composite material after obtaining lithium sulfide cladding;
Step 2: the nano-attapulgite stone based on molfraction, under ar gas environment, after the lithium sulfide cladding that step 1 is obtained Composite material, 0 ~ 30 part of P2S5, 0 ~ 30 part of SiS2, 0 ~ 30 part of GeS2, 0 ~ 30 part of B2S3, 0 ~ 30 part SnS, 0 ~ 30 part Al2S3, 0 ~ 30 part of P2S3, 0 ~ 30 part of Ga2S3, 0 ~ 30 part of ZnS, 0 ~ 30 part of As2S5, 0 ~ 10 part of P2O5, 0 ~ 10 part Li4SiO4, 0 ~ 10 part of Li3N, 0 ~ 10 part of Li3MO3, 0 ~ 10 part of GeO2, 0 ~ 10 part of GeSe2, 0 ~ 10 part of LiX, worn into after being sufficiently mixed Powder obtains A system, the A system is added in quartz ampoule, after vacuum sealing, 200 DEG C ~ 600 DEG C 2 ~ 6 h of heating are answered Condensation material, the composite material be sulfide electrolyte coat nano-attapulgite stone composite material, wherein M be B, Al, Ga or In, X is one of halogens.
A kind of lithium ion battery containing above-mentioned composite material, the anode of the lithium ion battery, electrolyte, in cathode At least one include the composite material.
Further, the cathode includes negative current collector, and the negative current collector surface is coated with active material, The active material contains the composite material, and the surface of the active material is coated with one layer of active lithium storage materials plating Layer I.
Further, the negative current collector surface is coated with one layer of active lithium storage materials coating II, the activity storage lithium material Expect coating II between the negative current collector and active material.
Further, the thickness of the active lithium storage materials coating I and active lithium storage materials coating II be 10nm ~ 100nm, the active material with a thickness of 1 ~ 5um.
Further, the active lithium storage materials in the active lithium storage materials coating I and active lithium storage materials coating II are equal For one of bismuth, lithium, silicon, tin, antimony, germanium, aluminium, lead, titanium, iron, chromium, molybdenum, nickel, gold, zinc or multiple combinations.
Further, the active material further includes binder and negative electrode active material.
Beneficial effects of the present invention:
The present invention be different from it is traditional lead lithium material, using the method fired after ball milling mixing, lithium sulfide electrolyte is led in preparation Material coats nano-attapulgite stone solid electrolyte.It is formed to have under certain reaction condition and leads lithium sulfide electrolyte material packet The nano bar-shape attapulgite structure covered, which, which leads lithium material, has the function of good to lead lithium and lithium is led on the rodlike surface Material, which has, continuously leads lithium structure.
Natural attapulgite is that a kind of crystalloid is hydrated alumina magnesia silicate, has unique layer chain structure feature, There are crystal lattice in its structure, rhabdolith is in needle-shaped, fibrous or fiber Set Status.Natural attapulgite crystal habit In rodlike, stick crystalline substance long 1-5um, wide 20-70nm, it is natural nano structure club shaped structure mineral material and performance stabilization, is good Load material.
Nano-attapulgite stone is the natural nano attapulgite exchanged through organically-modified or lithium cation, and sulfide is electrolysed Matter is coated on nano-attapulgite stone surface, can form one layer of high speed lithium ion tunnel on nano-attapulgite stone surface.Sulfide The nano-attapulgite stone structure of electrolyte cladding has bar-shaped nanostructure, especially in composite solid lithium-ion electrolyte, solid-state In lithium ion anode and lithium-ion negative pole, the formed therein which effect heap of nano-attapulgite stone structure of sulfide electrolyte cladding Product can improve composite solid lithium-ion electrolyte, solid lithium ion anode, lithium ion transport in lithium-ion negative pole, can be with Improve the mechanical property of composite material, there is industrial application value.
At the same time, coating thickness, packet can be controlled by ball milling burning process and covering material etc. in the invention Cladding material type can improve the nano-attapulgite stone material property of sulfide electrolyte cladding in a certain range, promote material The lithium ion transport performance and stability of material.Nano-attapulgite stone composite material is coated using sulfide electrolyte in the present invention, Using nano-attapulgite stone as carrier in electrodes of lithium-ion batteries, formation is rodlike continuously quickly to lead lithium channel, can effectively improve pole The transmission of lithium ion in piece, especially high quality energy density solid lithium ion battery anode, high-energy density lithium from There is good application potential in the cathode of sub- battery.
Detailed description of the invention
Fig. 1 is composite negative pole structural schematic diagram.
Fig. 2 is composite structure schematic diagram.
In figure: 1, negative current collector, 2, active lithium storage materials coating II, 3, active material, 4, composite material, 5, work Property lithium storage materials coating I, 41, sulfide electrolyte, 42, nano-attapulgite stone.
Specific embodiment
With reference to the accompanying drawings 1 and 2, by specific embodiment, the present invention is described further, following specific embodiments In, " drying " and " compacting " being related in the step of preparing anode pole piece, cathode pole piece and electrolyte belongs to the normal of this field Advise research technique.
Specific embodiment one
A kind of composite material, the composite material include sulfide electrolyte 41 and nano-attapulgite stone 42, the sulfide electricity It solves matter 41 and coats nano-attapulgite stone 42.
Further, thickness≤20um of the sulfide electrolyte 41,41 lithium ion conductivity of sulfide electrolyte The order of magnitude is 10-5S/cm to 10-2 S/cm;The nano-attapulgite stone 42 is commercialization nano-attapulgite stone, and the nanometer is recessed The stick of convex stick stone 42 brilliant long 100nm-50um, wide 10nm-120nm.
Further, the sulfide electrolyte 41 is one of following substance or a variety of combinations: aLi2S·b P2S5CLiX, wherein X represents halogens, 20≤a≤80,20≤b≤40,0≤c≤20;aLi2S·bP2S5CMeS, Middle Me is Si, Ge, Sn, Al or B, 20≤a≤80,20≤b≤40,0≤c≤20;aLi2S·bP2S5·cP2O5, wherein 67 < a < 80,0 < b < 40,0 < c < 25;Li4-aSi1-aPaS4, wherein 0 < a < 1;70Li2S·(30−a)P2S5·aP2S3, wherein 0 < a < 30;aLi2S·bSiS2, wherein 50≤a≤70,30≤b≤50;Li4-aSi1-aAlaS4, wherein 0 < a < 1;aLi2S· bSiS2·cLi3MO3, wherein M=B, Al, Ga or In, 20≤a≤80,20≤b≤40,0≤c≤20;aLi2S·bSiS2· cLi3N, wherein 20≤a≤80,20≤b≤40,0≤c≤20;aLi2S·bGeS2, wherein 0 < a < 60,40 < b < 100; 0.5Li2S·0.5[(1-a)GeS2·aGeO2], wherein 0 < a < 1;Li4+a (Ge1-aGab)S4, wherein 0 < a < 1,1 < b < 2;LiaGebPcS4, wherein 3≤a≤3.3,0≤b≤0.3,0.7≤c≤1.0;a(0.6Li2S·0.4SiS2)·bLi4SiO4, Wherein 80≤a≤100,0≤b≤20;LiaGebSecPdSe, wherein 3 < a < 4,0 < b < 1,0 < c < 2,0 < d < 1,2 < e < 4;LiaGebAscS4, wherein 3≤a≤3.5,0≤b≤0.5,0≤c≤0.5;LiaZnbGeS4, wherein 0 < a < 2,0 < b < 2;aLi2S·bP2S5·cGeS2·dSnSe2, wherein 20≤a≤80,20≤b≤40,0≤c≤10,0≤d≤10.
A kind of preparation method of composite material, comprising the following steps:
Step 1: based on molfraction, under ar gas environment, 40 ~ 100 parts of Li is weighed2S is dissolved in dehydrated alcohol, is added After 1.50 ~ 80.00 parts of nano-attapulgite stones are sufficiently impregnated bubble, are vacuumized under ar gas environment or under room temperature, be then heated to 50 ~ 90 DEG C, solvent absolute ethyl alcohol is removed, the nano-attapulgite stone composite material after obtaining lithium sulfide cladding;
Step 2: the nano-attapulgite stone based on molfraction, under ar gas environment, after the lithium sulfide cladding that step 1 is obtained Composite material, 0 ~ 30 part of P2S5、0~36 partsSiS2, 0 ~ 30 part of GeS2, 0 ~ 30 part of B2S3, 0 ~ 30 part SnS, 0 ~ 30 part Al2S3, 0 ~ 30 part of P2S3, 0 ~ 30 part of Ga2S3, 0 ~ 30 part of ZnS, 0 ~ 30 part of As2S5, 0 ~ 10 part of P2O5、0~ 10Li4SiO4, 0 ~ 10 part of Li3N, 0 ~ 10 part of Li3MO3, (M B, Al, Ga or In), 0 ~ 10 part of GeO2, 0 ~ 10 part of GeSe2、0~10 Part LiX(X is one of halogens), they are put into togerther in the alms bowl of zirconium oxide with zirconia ball, in ar gas environment Under closed alms bowl, which is installed on ball mill, is rotated with the speed of 200r/min ~ 800r/min, 10 ~ 50h is mixed, is filled Divide mixed A system, the A system mixed-powder is added in quartz ampoule, is heated after vacuum sealing, heating temperature is 200 DEG C ~ 600 DEG C, heating time is 2 ~ 6 h, obtains composite material, and the composite material is that sulfide electrolyte cladding nanometer is recessed Convex stick stone composite material.
A kind of lithium ion battery containing the composite material, the anode of the lithium ion battery, electrolyte, in cathode At least one includes the composite material.
Further, the cathode includes negative current collector 1, and 1 surface of negative current collector is coated with composite reactive object Matter 3, the active material 3 have included the composite material 4, and the surface of the active material 3 is coated with one layer of activity Lithium storage materials coating I 5.
Further, 1 surface of negative current collector is coated with one layer of active lithium storage materials coating II 2, the activity storage lithium Material coating II 2 is between the negative current collector 1 and active material 3.
Further, the thickness of the active lithium storage materials coating I 5 and active lithium storage materials coating II 2 be 10 ~ 100nm, the active material 3 with a thickness of 1 ~ 5um.
Further, the active lithium storage materials in the active lithium storage materials coating I 5 and active lithium storage materials coating II 2 It is one of bismuth, lithium, silicon, tin, antimony, germanium, aluminium, lead, titanium, iron, chromium, molybdenum, nickel, gold, zinc or multiple combinations.
Further, the active material 3 further includes binder and negative electrode active material.
Further, the negative current collector 1 is copper foil.
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in lithium ion cell positive: pressing mass parts 40 ~ 96 parts of positive active material, 1 ~ 10 part of binder, 0 ~ 20 part are led lithium material, 1 ~ 10 part of conductive agent, on 0.5 ~ 5 part by meter It states sulfide electrolyte cladding nano-attapulgite stone composite material after evenly mixing, forms positive pole after coated dry compacting Piece, the anode pole piece can be used for solid lithium ion battery, and wherein positive active material includes LiFePO4, cobalt acid lithium, nickel cobalt manganese The combination of one or more of ternary battery material, LiMn2O4, nickel cobalt aluminium ternary battery material, sulphur.Binder be PVDF, At least one of PVDF-HFP, oil system butylbenzene binder, polyimides, polyamide-imides lead lithium material as vulcanization object It is at least one of electrolyte, oxide system electrolyte, polymeric system electrolyte;Conductive agent be conductive carbon black and/or Carbon nanotube.
Sulfide electrolyte coats nano-attapulgite stone composite material in the application of lithium ion battery solid electrolyte: pressing matter Part meter is measured, 80 parts ~ 100 parts solid electrolytes, 1 part ~ 10 parts sulfide electrolyte cladding nano-attapulgite stone composite materials are equal Even mixing is prepared into solid electrolyte after coated compacting, wherein solid electrolyte include sulfide systems, oxide system, Polymeric system.
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in negative electrode of lithium ion battery: pressing mass parts 10 parts ~ 20 parts sulfide electrolyte are coated nano-attapulgite stone composite material, 0.5 part ~ 5 parts binders, 10 parts ~ 20 parts by meter Negative electrode active material after evenly mixing, is coated on negative current collector, after dry compacting, by active lithium storage materials on its surface Vacuum Deposition is carried out, thickness of coating is 10 ~ 100nm, obtains the ultra-thin composite negative pole with a thickness of 8 ~ 20um.Wherein negative pole currect collecting Body can be the copper foil after copper foil or progress Vacuum Deposition activity lithium storage materials.Wherein binder is butylbenzene binder, polyacrylic acid At least one of ester binder.Wherein negative electrode active material be carbon material, bismuth metal, lithium metal, nitride, silica-base material, Tin-based oxide, kamash alloy, antimony-containing alloy, germanium-base alloy, acieral, lead-containing alloy, titanyl compound, is received stannide Rice transition metal oxide MO (M=Co, Ni, Cu, Fe), the oxide of iron, the oxide of chromium, the oxide of molybdenum, in phosphide One or more combinations.Wherein active lithium storage materials be bismuth, lithium, silicon, tin, antimony, germanium, aluminium, lead, titanium, iron, chromium, molybdenum, nickel, gold, One of zinc or multiple combinations.The composite negative pole is mainly used for high volume energy density lithium ion battery.
Below by specific embodiment, the present invention is further illustrated.Reagent, the material arrived used in following the description Material and instrument such as not special explanation, are conventional reagent, conventional material and conventional instrument, commercially available, institute The reagent being related to can also be synthesized by conventional synthesis process and be obtained.
Embodiment 1
A kind of preparation method of composite material, comprising the following steps:
Step 1: based on molfraction, under ar gas environment, 40 parts of Li is weighed2S is dissolved in dehydrated alcohol, is added 1.50 After part nano-attapulgite stone is sufficiently impregnated bubble, vacuumize process under room temperature is then heated to 50 DEG C, removes solvent absolute ethyl alcohol, Nano-attapulgite stone composite material after obtaining lithium sulfide cladding;
Step 2: the nano-attapulgite stone based on molfraction, under ar gas environment, after the lithium sulfide cladding that step 1 is obtained Composite material, 13.5 parts of P2S5, they are put into togerther in the alms bowl of zirconium oxide with zirconia ball, it is closed under ar gas environment The alms bowl is installed on ball mill by alms bowl, is rotated with the speed of 200r/min, 20 h of mixing, the A system after being sufficiently mixed, The A system mixed-powder is added in quartz ampoule, is heated after vacuum sealing, heating temperature is 400 DEG C, and heating time is 2 h obtain composite material, and the composite material is that sulfide electrolyte coats nano-attapulgite stone composite material, wherein vulcanizing Object electrolyte is 75Li2S·25P2S5
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in lithium ion cell positive: pressing mass parts 40 parts of positive active material, 1 part of binder, 1 part of conductive agent, 0.5 part of above-mentioned sulfide electrolyte are coated nano concavo-convex by meter Stick stone composite material after evenly mixing, forms anode pole piece after coated dry compacting, the anode pole piece can be used for solid-state lithium from Sub- battery, wherein positive active material is nickel-cobalt-manganese ternary battery material, and binder PVDF, conductive agent is carbon nanotube.
Sulfide electrolyte coats nano-attapulgite stone composite material in the application of lithium ion battery solid electrolyte: pressing matter Part meter is measured, 80 parts of solid electrolytes, 1 part of sulfide electrolyte cladding nano-attapulgite stone composite material are uniformly mixed, through applying It is prepared into solid electrolyte after cloth compacting, wherein solid electrolyte includes sulfide systems, oxide system, polymeric system.
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in negative electrode of lithium ion battery: pressing mass parts Meter, 10 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials, 0.5 part of binder, 10 parts of negative electrode active materials are equal It after even mixing, is coated on negative current collector, after dry compacting, active lithium storage materials is subjected to Vacuum Deposition on its surface, Thickness of coating is 10nm, obtains the ultra-thin composite negative pole with a thickness of 8um.Wherein negative current collector can be true for copper foil or progress Sky plates the copper foil after active lithium storage materials.Wherein binder is butylbenzene binder.Wherein negative electrode active material is carbon material.Wherein Active lithium storage materials are bismuth.The composite negative pole is mainly used for lithium ion battery with high energy density.
Embodiment 2
A kind of preparation method of composite material, comprising the following steps:
Step 1: based on molfraction, under ar gas environment, 100 parts of Li is weighed2S is dissolved in dehydrated alcohol, is added After 80.00 parts of nano-attapulgite stones are sufficiently impregnated bubble, it is heated to 90 DEG C under ar gas environment, removes etoh solvent, is vulcanized Nano-attapulgite stone composite material after lithium cladding;
Step 2: the nano-attapulgite stone based on molfraction, under ar gas environment, after the lithium sulfide cladding that step 1 is obtained Composite material, 30 parts of P2S5, 3 parts of LiBr, they and zirconia ball are put into togerther in the alms bowl of zirconium oxide, in ar gas environment Under closed alms bowl, which is installed on ball mill, is rotated with the speed of 300r/min, 30h, the A after being sufficiently mixed are mixed The A system mixed-powder is added in quartz ampoule, is heated after vacuum sealing by system, and heating temperature is 300 DEG C, heating Time is 6 h, obtains composite material, and the composite material is that sulfide electrolyte coats nano-attapulgite stone composite material, Middle sulfide electrolyte is 100Li2S·30P2S5·3LiBr。
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in lithium ion cell positive: pressing mass parts Meter, leads lithium material, 3 parts of conductive agents, 3 parts of above-mentioned sulfide electrolyte packets for 50 parts of positive active material, 2 parts of binders, 1 part It covers nano-attapulgite stone composite material after evenly mixing, forms anode pole piece after coated dry compacting, the anode pole piece is available In solid lithium ion battery, wherein positive active material is nickel cobalt aluminium ternary battery material, and binder is oil system butylbenzene binder, Leading lithium material is sulfide systems electrolyte, and conductive agent is conductive carbon black.
Sulfide electrolyte coats nano-attapulgite stone composite material in the application of lithium ion battery solid electrolyte: pressing matter Part meter is measured, 100 parts of solid electrolytes, 10 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials are uniformly mixed, are passed through It is prepared into solid electrolyte after coating compacting, wherein solid electrolyte includes sulfide systems, oxide system, polymeric acceptor System.
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in negative electrode of lithium ion battery: pressing mass parts Meter, 12 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials, 4 parts of binders, 12 parts of negative electrode active materials are uniform It after mixing, is coated on negative current collector, after dry compacting, active lithium storage materials is subjected to Vacuum Deposition, plating on its surface Layer obtains the ultra-thin composite negative pole with a thickness of 10um with a thickness of 30nm.Wherein negative current collector can be copper foil or progress vacuum Copper foil after plating active lithium storage materials.Wherein binder is polyacrylate binder.Wherein negative electrode active material can be tin Compound.Wherein active lithium storage materials are lithium.The composite negative pole is mainly used for lithium ion battery with high energy density.
Embodiment 3
A kind of preparation method of composite material, comprising the following steps:
Step 1: based on molfraction, under ar gas environment, 70 parts of Li is weighed2S is dissolved in dehydrated alcohol, is added 50.00 After part nano-attapulgite stone is sufficiently impregnated bubble, vacuumize process under room temperature is then heated to 60 DEG C, removes etoh solvent, obtains Nano-attapulgite stone composite material after lithium sulfide cladding;
Step 2: the nano-attapulgite stone based on molfraction, under ar gas environment, after the lithium sulfide cladding that step 1 is obtained Composite material, 28 parts of P2S5, 3 parts of P2O5, they are put into togerther in the alms bowl of zirconium oxide with zirconia ball, in ar gas environment Under closed alms bowl, which is installed on ball mill, is rotated with the speed of 800r/min, 10h, the A after being sufficiently mixed are mixed The A system mixed-powder is added in quartz ampoule, is heated after vacuum sealing by system, and heating temperature is 200 DEG C, heating Time is 3 hours, obtains composite material, and the composite material is that sulfide electrolyte coats nano-attapulgite stone composite material, Wherein sulfide electrolyte is 70Li2S·28P2S5·3P2O5
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in lithium ion cell positive: pressing mass parts 60 parts of positive active material, 4 parts of binders, 5 parts are led lithium material, 4 parts of conductive agents, 1 part of above-mentioned sulfide electrolyte packet by meter It covers nano-attapulgite stone composite material after evenly mixing, forms anode pole piece after coated dry compacting, the anode pole piece is available In solid lithium ion battery, wherein positive active material is LiFePO4, and binder is polyimides, and leading lithium material is oxide System electrolyte;Conductive agent is carbon nanotube.
Sulfide electrolyte coats nano-attapulgite stone composite material in the application of lithium ion battery solid electrolyte: pressing matter Part meter is measured, 90 parts of solid electrolytes, 6 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials are uniformly mixed, through applying It is prepared into solid electrolyte after cloth compacting, wherein solid electrolyte includes sulfide systems, oxide system, polymeric system.
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in negative electrode of lithium ion battery: pressing mass parts Meter, 18 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials, 1 part of binder, 16 parts of negative electrode active materials are uniform It after mixing, is coated on negative current collector, after dry compacting, active lithium storage materials is subjected to Vacuum Deposition, plating on its surface Layer obtains the ultra-thin composite negative pole with a thickness of 12um with a thickness of 40nm.Wherein negative current collector can be copper foil or progress vacuum Copper foil after plating active lithium storage materials.Wherein binder is polyacrylate binder.Wherein negative electrode active material is nitride. Wherein active lithium storage materials are lithium.The composite negative pole is mainly used for lithium ion battery with high energy density.
Embodiment 4
A kind of preparation method of composite material, comprising the following steps:
Step 1: based on molfraction, under ar gas environment, 76.75 parts of Li is weighed2S is dissolved in dehydrated alcohol, is added After 60.00 parts of nano-attapulgite stones are sufficiently impregnated bubble, room temperature vacuumize process is then heated to 70 DEG C, removes etoh solvent, obtains Nano-attapulgite stone composite material to after lithium sulfide cladding;
Step 2: the nano-attapulgite stone based on molfraction, under ar gas environment, after the lithium sulfide cladding that step 1 is obtained Composite material, 36 parts of SiS2, 5.5 parts of P2S5, 10 parts of Li4SiO4, 10 parts of Li3N, 10 parts of Li3AlO3, 1 part of LiCl, 1 part P2S3, they are put into togerther in the alms bowl of zirconium oxide with zirconia ball, which is installed on ball by the closed alms bowl under ar gas environment It on grinding machine, is rotated with the speed of 400r/min, mixes 40h, the A system after being sufficiently mixed, by the A system mixed-powder It being added in quartz ampoule, is heated after vacuum sealing, heating temperature is 500 DEG C, and heating time is 4 hours, composite material is obtained, The composite material is that sulfide electrolyte coats nano-attapulgite stone composite material, and wherein sulfide electrolyte is 20 (0.6Li2S·0.4SiS2)·10Li4SiO4、22(0.75Li2S·0.25P2S5)·P2S3、20(0.6Li2S·0.4SiS2)· LiCl、30(0.6Li2S·0.4SiS2)·10Li3AlO3、20(0.6Li2S·0.4SiS2)·10Li3The mixture of N.
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in lithium ion cell positive: pressing mass parts 96 parts of positive active material, 10 parts of binders, 20 parts are led lithium material, 10 parts of conductive agents, 5 parts of above-mentioned sulfide and are electrolysed by meter Matter coats nano-attapulgite stone composite material after evenly mixing, forms anode pole piece after coated dry compacting, the anode pole piece It can be used for solid lithium ion battery, wherein positive active material is cobalt acid lithium, and binder PVDF leads lithium material as vulcanization object It is electrolyte and oxide system electrolyte;Conductive agent is conductive carbon black and carbon nanotube.
Sulfide electrolyte coats nano-attapulgite stone composite material in the application of lithium ion battery solid electrolyte: pressing matter Part meter is measured, 85 parts of solid electrolytes, 8 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials are uniformly mixed, through applying It is prepared into solid electrolyte after cloth compacting, wherein solid electrolyte includes sulfide systems, oxide system, polymeric system.
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in negative electrode of lithium ion battery: pressing mass parts Meter, 20 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials, 5 parts of binders, 20 parts of negative electrode active materials are uniform It after mixing, is coated on negative current collector, after dry compacting, active lithium storage materials is subjected to Vacuum Deposition, plating on its surface Layer obtains the ultra-thin composite negative pole with a thickness of 20um with a thickness of 100nm.Wherein negative current collector can be true for copper foil or progress Sky plates the copper foil after active lithium storage materials.Wherein binder is butylbenzene binder.Wherein negative electrode active material can close for tinbase Gold.Wherein active lithium storage materials are bismuth.The composite negative pole is mainly used for lithium ion battery with high energy density.
Embodiment 5
A kind of preparation method of composite material, comprising the following steps:
Step 1: based on molfraction, under ar gas environment, 60 parts of Li is weighed2S is dissolved in dehydrated alcohol, is added 20.00 After part nano-attapulgite stone is sufficiently impregnated bubble, room temperature vacuumize process is then heated to 80 DEG C, removes etoh solvent, obtains sulphur Nano-attapulgite stone composite material after changing lithium cladding;
Step 2: the nano-attapulgite stone based on molfraction, under ar gas environment, after the lithium sulfide cladding that step 1 is obtained The P that 20 parts of composite material2S5, 4 parts of GeS2, 1 part of GeSe2, they are put into togerther in the alms bowl of zirconium oxide with zirconia ball, The closed alms bowl under ar gas environment, which is installed on ball mill, is rotated with the speed of 450r/min, and 50h is mixed, and is obtained sufficiently The A system mixed-powder is added in quartz ampoule, is heated after vacuum sealing, heating temperature is by mixed A system 600 DEG C, heating time is 5 hours, obtains composite material, and the composite material is that sulfide electrolyte coats nano-attapulgite stone Composite material, wherein sulfide electrolyte is 80(0.75Li2S·0.25P2S5) 4GeS2·GeSe2
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in lithium ion cell positive: pressing mass parts 90 parts of positive active material, 6 parts of binders, 10 parts are led lithium material, 6 parts of conductive agents, 5 parts of above-mentioned sulfide electrolyte by meter It coats nano-attapulgite stone composite material after evenly mixing, forms anode pole piece after coated dry compacting, which can For solid lithium ion battery, wherein positive active material includes nickel cobalt aluminium ternary battery material, and binder is viscous for oil system butylbenzene Agent is tied, leading lithium material is polymeric system electrolyte, and conductive agent is conductive carbon black.
Sulfide electrolyte coats nano-attapulgite stone composite material in the application of lithium ion battery solid electrolyte: pressing matter Part meter is measured, 95 parts of solid electrolytes, 9 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials are uniformly mixed, through applying It is prepared into solid electrolyte after cloth compacting, wherein solid electrolyte includes sulfide systems, oxide system, polymeric system.
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in negative electrode of lithium ion battery: pressing mass parts Meter, 14 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials, 2 parts of binders, 14 parts of negative electrode active materials are uniform It after mixing, is coated on negative current collector, after dry compacting, active lithium storage materials is subjected to Vacuum Deposition, plating on its surface Layer obtains the ultra-thin composite negative pole with a thickness of 16um with a thickness of 80nm.Wherein negative current collector can be copper foil or progress vacuum Copper foil after plating active lithium storage materials.Wherein binder is butylbenzene binder.Wherein negative electrode active material can be antimony-containing alloy. Wherein active lithium storage materials are aluminium.The composite negative pole is mainly used for lithium ion battery with high energy density.
Embodiment 6
A kind of preparation method of composite material, comprising the following steps:
Step 1: based on molfraction, under ar gas environment, 45 parts of Li is weighed2S is dissolved in dehydrated alcohol, is added 50.00 After part nano-attapulgite stone is sufficiently impregnated bubble, vacuumize process under room temperature is then heated to 85 DEG C, removes etoh solvent, obtains Nano-attapulgite stone composite material after lithium sulfide cladding;
Step 2: the nano-attapulgite stone based on molfraction, under ar gas environment, after the lithium sulfide cladding that step 1 is obtained Composite material, 15 parts of P2S5, 4 parts of SnS, 5 parts of Al2S3, 1 part of As2S5, 10 parts of Li3GaO3, 10 parts of Li3InO3, 10 parts 10 Li3BO3, they are put into togerther in the alms bowl of zirconium oxide with zirconia ball, the closed alms bowl under ar gas environment installs the alms bowl It on ball mill, is rotated with the speed of 500r/min, mixes 45h, the A system after being sufficiently mixed mixes the A system Powder is added in quartz ampoule, is heated after vacuum sealing, and heating temperature is 350 DEG C, and heating time is 6 hours, obtains compound Material, the composite material are that sulfide electrolyte coats nano-attapulgite stone composite material, and wherein sulfide electrolyte is 60 (0.75Li2S·0.25P2S5)·10Li3GaO3·10 Li3InO3·10Li3BO3·5Al2S3·4SnS·As2S5
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in lithium ion cell positive: pressing mass parts 50 parts of positive active material, 8 parts of binders, 15 parts are led lithium material, 9 parts of conductive agents, 4 parts of above-mentioned sulfide electrolyte by meter It coats nano-attapulgite stone composite material after evenly mixing, forms anode pole piece after coated dry compacting, which can For solid lithium ion battery, wherein positive active material is nickel-cobalt-manganese ternary battery material, and binder PVDF leads lithium material For oxide system electrolyte;Conductive agent is conductive carbon black.
Sulfide electrolyte coats nano-attapulgite stone composite material in the application of lithium ion battery solid electrolyte: pressing matter Part meter is measured, 88 parts of solid electrolytes, 7 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials are uniformly mixed, through applying It is prepared into solid electrolyte after cloth compacting, wherein solid electrolyte includes sulfide systems, oxide system, polymeric system.
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in negative electrode of lithium ion battery: pressing mass parts Meter, 16 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials, 3 parts of binders, 18 parts of negative electrode active materials are uniform It after mixing, is coated on negative current collector, after dry compacting, active lithium storage materials is subjected to Vacuum Deposition, plating on its surface Layer obtains the ultra-thin composite negative pole with a thickness of 15um with a thickness of 60nm.Wherein negative current collector can be copper foil or progress vacuum Copper foil after plating active lithium storage materials.Wherein binder is butylbenzene binder.Wherein negative electrode active material can be the oxidation of titanium Object.Wherein active lithium storage materials are zinc.The composite negative pole is mainly used for lithium ion battery with high energy density.
Embodiment 7
A kind of preparation method of composite material, comprising the following steps:
Step 1: based on molfraction, under ar gas environment, 52.5 parts of Li is weighed2S is dissolved in dehydrated alcohol, is added After 20.00 parts of nano-attapulgite stones are sufficiently impregnated bubble, room temperature vacuumize process is then heated to 55 DEG C, removes etoh solvent, obtains Nano-attapulgite stone composite material to after lithium sulfide cladding;
Step 2: the nano-attapulgite stone based on molfraction, under ar gas environment, after the lithium sulfide cladding that step 1 is obtained Composite material, 17.5 parts of P2S5, 25 parts of ZnS, 5 parts of GeO2, they are put into togerther to the alms bowl of zirconium oxide with zirconia ball In, which is installed on ball mill by the closed alms bowl under ar gas environment, is rotated with the speed of 700r/min, mixes 25h, obtains The A system mixed-powder is added in quartz ampoule, is heated after vacuum sealing, heating temperature by the A system after being sufficiently mixed It is 500 DEG C, heating time is 3 hours, obtains composite material, and the composite material is that sulfide electrolyte coats nano-attapulgite Stone composite material, wherein sulfide electrolyte is 70 (0.75Li2S·0.25P2S5)·25ZnS·5GeO2
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in lithium ion cell positive: pressing mass parts 55 parts of positive active material, 9 parts of binders, 8 parts are led lithium material, 8 parts of conductive agents, 2 parts of above-mentioned sulfide electrolyte packets by meter It covers nano-attapulgite stone composite material after evenly mixing, forms anode pole piece after coated dry compacting, the anode pole piece is available In solid lithium ion battery, wherein positive active material is cobalt acid lithium, and binder PVDF, leading lithium material is sulfide systems electricity Xie Zhi;Conductive agent is carbon nanotube.
Sulfide electrolyte coats nano-attapulgite stone composite material in the application of lithium ion battery solid electrolyte: pressing matter Part meter is measured, 96 parts of solid electrolytes, 3 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials are uniformly mixed, through applying It is prepared into solid electrolyte after cloth compacting, wherein solid electrolyte includes sulfide systems, oxide system, polymeric system.
Sulfide electrolyte coats application of the nano-attapulgite stone composite material in negative electrode of lithium ion battery: pressing mass parts Meter, 15 parts of sulfide electrolyte cladding nano-attapulgite stone composite materials, 4 parts of binders, 16 parts of negative electrode active materials are uniform It after mixing, is coated on negative current collector, after dry compacting, active lithium storage materials is subjected to Vacuum Deposition, plating on its surface Layer obtains the ultra-thin composite negative pole with a thickness of 18um with a thickness of 50nm.Wherein negative current collector can be copper foil or progress vacuum Copper foil after plating active lithium storage materials.Wherein binder is butylbenzene binder.Wherein negative electrode active material can be carbon material.Its Middle activity lithium storage materials are lithium.The composite negative pole is mainly used for lithium ion battery with high energy density.
The sulfide electrolyte and commercial polymer polyethylene oxide electrolyte that Examples 1 to 7 is prepared carry out Conductivity at room temperature rate, lithium ion transference number test, test result is as follows shown in table.
Conductivity it can be seen from the result of upper table under conventional polyethylene oxide polymer electrolyte room temperature is 1.26 ×10-5S/cm, lithium ion transference number 0.38, sulfide electrolyte prepared by the present invention coat nano-attapulgite stone composite material Conductivity under room temperature is about 10-3S/cm or so is compared with polymeric system has more superior conductivity at room temperature and lithium Transference number of ions has preferable lithium ion transport with the nano-attapulgite stone club shaped structure surface of sulfide electrolyte cladding Channel can effectively improve the performance of lithium ion battery.Sulfide electrolyte of the invention coats nano-attapulgite stone structure, passes through Clad sulfide electrolyte is designed, the sulfide electrolyte cladding concave convex rod that lithium ion conductivity is high, performance is stable can be obtained The nano-attapulgite stone of stone structure, sulfide electrolyte cladding has good application in lithium ion battery with high energy density Prospect.

Claims (10)

1. a kind of composite material, it is characterised in that: the composite material includes sulfide electrolyte (41) and nano-attapulgite stone (42), sulfide electrolyte (41) cladding nano-attapulgite stone (42).
2. a kind of composite material according to claim 1, it is characterised in that: sulfide electrolyte (41) clad Thickness≤20um, nano-attapulgite stone (42) stick brilliant long 100nm-50um, wide 10nm-120nm.
3. a kind of composite material according to claim 1, it is characterised in that: the sulfide electrolyte (41) is following object One of matter or a variety of combinations: aLi2S·b P2S5CLiX, wherein X represents halogens, and 20≤a≤80,20≤b≤ 40,0≤c≤20;aLi2S·bP2S5CMeS, wherein Me is Si, Ge, Sn, Al or B, 20≤a≤80,20≤b≤40,0≤c ≤20;aLi2S·bP2S5·cP2O5, wherein 67 < a < 80,0 < b < 40,0 < c < 25;Li4-aSi1-aPaS4, wherein 0 < a < 1;70Li2S·(30−a)P2S5·aP2S3, wherein 0 < a < 30;aLi2S·bSiS2, wherein 50≤a≤70,30≤b≤ 50;Li4-aSi1-aAlaS4, wherein 0 < a < 1;aLi2S·bSiS2·cLi3MO3, wherein M=B, Al, Ga or In, 20≤a≤80, 20≤b≤40,0≤c≤20;aLi2S·bSiS2·cLi3N, wherein 20≤a≤80,20≤b≤40,0≤c≤20; aLi2S·bGeS2, wherein 0 < a < 60,40 < b < 100;0.5Li2S·0.5[(1-a)GeS2·aGeO2], wherein 0 < a < 1;Li4+a (Ge1-aGab)S4, wherein 0 < a < 1,1 < b < 2;LiaGebPcS4, wherein 3≤a≤3.3,0≤b≤0.3,0.7≤ c≤1.0;a(0.6Li2S·0.4SiS2)·bLi4SiO4, wherein 80≤a≤100,0≤b≤20;LiaGebSecPdSe, wherein 3 < a < 4,0 < b < 1,0 < c < 2,0 < d < 1,2 < e < 4;LiaGebAscS4, wherein 3≤a≤3.5,0≤b≤0.5,0≤ c≤0.5;LiaZnbGeS4, wherein 0 < a < 2,0 < b < 2;aLi2S·bP2S5·cGeS2·dSnSe2, wherein 20≤a≤80, 20≤b≤40、0≤c≤10、0≤d≤10。
4. a kind of preparation method of composite material described in claim 1-3 any claim, which is characterized in that including following Step:
Step 1: based on molfraction, under ar gas environment, 40 ~ 100 parts of Li is weighed2S is dissolved in dehydrated alcohol, is added After 1.50 ~ 80.00 parts of nano-attapulgite stones are sufficiently impregnated bubble, under ar gas environment or room temperature vacuumize process, it is then heated to 50 ~ 90 DEG C, solvent absolute ethyl alcohol is removed, the nano-attapulgite stone composite material after obtaining lithium sulfide cladding;
Step 2: the nano-attapulgite stone based on molfraction, under ar gas environment, after the lithium sulfide cladding that step 1 is obtained Composite material, 0 ~ 30 part of P2S5, 0 ~ 30 part of SiS2, 0 ~ 30 part of GeS2, 0 ~ 30 part of B2S3, 0 ~ 30 part SnS, 0 ~ 30 part Al2S3, 0 ~ 30 part of P2S3, 0 ~ 30 part of Ga2S3, 0 ~ 30 part of ZnS, 0 ~ 30 part of As2S5, 0 ~ 10 part of P2O5, 0 ~ 10 part Li4SiO4, 0 ~ 10 part of Li3N, 0 ~ 10 part of Li3MO3, 0 ~ 10 part of GeO2, 0 ~ 10 part of GeSe2, 0 ~ 10 part of LiX, worn into after being sufficiently mixed Powder obtains A system, the A system is added in quartz ampoule, after vacuum sealing, 200 DEG C ~ 600 DEG C 2 ~ 6 h of heating are answered Condensation material, the composite material be sulfide electrolyte coat nano-attapulgite stone composite material, wherein M be B, Al, Ga or In, X is one of halogens.
5. a kind of lithium ion battery containing composite material described in claim 1-3 any claim, it is characterised in that: institute Stating at least one of anode, electrolyte, cathode of lithium ion battery includes the composite material.
6. a kind of lithium ion battery according to claim 5, the cathode includes negative current collector (1), it is characterised in that: Negative current collector (1) surface is coated with active material (3), and the active material (3) contains the composite wood Expect (4), the surface of the active material (3) is coated with one layer of active lithium storage materials coating I (5).
7. a kind of lithium ion battery according to claim 6, it is characterised in that: negative current collector (1) surface is coated with One layer of active lithium storage materials coating II (2), the activity lithium storage materials coating II (2) are located at the negative current collector (1) and answer It closes between active material (3).
8. a kind of lithium ion battery according to claim 7, it is characterised in that: it is described activity lithium storage materials coating I (5) and The thickness of active lithium storage materials coating II (2) is 10nm ~ 100nm, the active material (3) with a thickness of 1 ~ 5um.
9. a kind of lithium ion battery according to claim 7, it is characterised in that: it is described activity lithium storage materials coating I (5) and Active lithium storage materials in active lithium storage materials coating II (2) be bismuth, lithium, silicon, tin, antimony, germanium, aluminium, lead, titanium, iron, chromium, molybdenum, One of nickel, gold, zinc or multiple combinations.
10. a kind of lithium ion battery according to claim 7, it is characterised in that: the active material (3) further includes Binder and negative electrode active material.
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