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 PDFInfo
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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
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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| CB03 | Change of inventor or designer information |
Inventor after: Tang Weichao Inventor after: Li Suli Inventor after: Zhao Wei Inventor after: Yuan Hao Inventor after: Li Junyi Inventor after: Xu Yanming Inventor after: Gao Yunzhi Inventor before: Tang Weichao Inventor before: Li Suli Inventor before: Zhao Wei Inventor before: Yuan Hao Inventor before: Li Junyi Inventor before: Xu Yanming |
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| GR01 | Patent grant | ||
| GR01 | Patent grant |