CN109712823A - Solid glass electrolyte and its combination electrode material, diaphragm, electrode slice and all-solid-state supercapacitor - Google Patents
Solid glass electrolyte and its combination electrode material, diaphragm, electrode slice and all-solid-state supercapacitor Download PDFInfo
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Abstract
The present invention relates to solid glass electrolyte and combination electrode material, solid glass electrolyte membrane, electrode slice and all-solid-state supercapacitors.The chemical formula of solid glass electrolyte is Li3+x‑ 2yMyA1+z‑wB1+x‑2z‑2wOr Li3+x‑2yMyA1+z‑wB1+x‑2z‑2w‑nbDb, solid electrolyte material conductivity with higher proposed by the present invention, meanwhile, supercapacitor production method by solid glass electrolyte precursor method directly positive or negative pole active material with closely merge, reach the conductive network as liquid electrolyte.Simultaneously, close double electrical layers are formed in positive and negative electrode active material and solid glass electrolyte two-phase interface, greatly improve lithium ion diffusion and insertion, abjection ability, overcome the solid electrolyte conductivity generally disadvantage lower than liquid electrolyte, with low internal resistance, to realize the high power characteristic of lithium ion all-solid-state supercapacitor.Technical feasibility of the invention is high, and production stage is simple, can be used for being mass produced.
Description
[technical field]
The present invention relates to solid glass electrolyte and its combination electrode material, diaphragm, electrode slice and all solid state super capacitors
Device.
[background technique]
All-solid-state supercapacitor is due to good flexible, electroless liquid leakage and can to realize ultra-thin shape etc. excellent
Point, in industry and consumer fields such as communication science and technology, information technology, household electrical appliance, electric car, aerospaces, especially intelligently
Wearable field has broad application prospects.Solid electrolyte material has much at present, but the ion of solid electrolyte material
Conductivity is generally below 1 × 10-3Scm-1, the lower problem of generally existing Conductivity Ratio, this also leads to the internal resistance of supercapacitor
It is larger, the power characteristic of supercapacitor is influenced, seriously constrains supercapacitor in high-power application, this will be weakened greatly
The application advantage of supercapacitor.
On the other hand, common all-solid-state supercapacitor production is not considered how positive and negative electrode active material
Combined problem well with solid electrolyte, often simply by anode pole piece, cathode pole piece, solid electrolyte membrane (or
Increase by one layer of diaphragm) it stacks, then also need to be added a small amount of liquid electrolyte, active material inside such supercapacitor
Contacted with solid electrolyte ideal not as good as liquid, contact resistance is big, cause the power density of supercapacitor monomer significantly under
Drop, influences its application.
[summary of the invention]
The main purpose of the present invention is to provide a kind of solid glass electrolyte, and use the solid glass electrolyte system
Compound positive and negative electrode material, positive and negative plate, solid electrolyte membrane and the all-solid-state supercapacitor made.
To achieve the goals above, a kind of solid glass electrolyte, chemical formula Li have been invented first3+x-2yMyA1+z- wB1+x-2z-2w,
Wherein:
M chemical valence is+2, is one kind in Mg, Ca, Sr, Ba, Ge, La, Ti, Zr, Zn, Ni element, and A chemical valence is -2, is
O, one of S or Se,
B chemical valence is -1, is one of F, Cl, Br or I,
0 < x≤1,0≤y≤0.1,0≤z < 1,0≤w < 1, and w≤x.
Above-mentioned solid glass electrolyte is preferably Li2.99Ba0.005OCl。
The invention also includes another solid glass electrolyte, chemical formula Li3+x-2yMyA1+z-wB1+x-2z-2w-nbDb,
Wherein:
M chemical valence is+2, is one kind in Mg, Ca, Sr, Ba, Ge, La, Ti, Zr, Zn, Ni element, and A chemical valence is -2, is
O, one of S or Se,
B chemical valence is -1, is one of F, Cl, Br or I,
D chemical valence is-n, is selected from OH-、PF6 -、BF4 -、CO3 2-、CF3SO3 -、CH3 -、CH3CO2 -、ClO2 -、ClO3 -、ClO4 -、
H2PO4 -、HCO3 -、HF2 -、HSO4 -、IO3 -、IO4 -、NH2 -、NH2CH2COO-、NO3 -、PO3 -、S6 -、SCN-、B(OH)4 -、SO3F-And N3-
One of or it is a variety of,
0 < x≤1,0≤y≤0.1,0≤z < 1,0≤w < 1, and w≤x, 0≤b < 1, and b≤(2z-2w-x)/n.
The invention also includes a kind of composite positive poles, including positive active material particle, in positive active material particle
Surface recombination has an any description above solid glass electrolyte, it is described it is compound be the solid glass electrolyte presoma it is same
What positive active material particle was directly formed after vacuum heat treatment between 200 DEG C~500 DEG C together.
It further preferably include conductive agent in composite positive pole.
The solid glass electrolyte preferably accounts for the 2~60% of composite positive pole total weight.
The invention also includes a kind of composite negative pole materials, including anode active material particles, in anode active material particles
Surface recombination has an any description above solid glass electrolyte, it is described it is compound be the solid glass electrolyte presoma it is same
What anode active material particles were directly formed after vacuum heat treatment between 200 DEG C~500 DEG C together.
It further preferably include conductive agent in composite positive pole.
The solid glass electrolyte preferably accounts for the 2~60% of composite negative pole material total weight.
The invention also includes a kind of preparation method of composite positive pole, before any description above solid glass electrolyte
It drives body and is formed directly into positive electrode active material after vacuum heat treatment between 200 DEG C~500 DEG C together with positive active material particle
Matter particle surface.
The invention also includes a kind of preparation method of composite negative pole material, before any description above solid glass electrolyte
It drives body and is formed directly into negative electrode active material after vacuum heat treatment between 200 DEG C~500 DEG C together with anode active material particles
Matter particle surface.
The invention also includes a kind of solid glass electrolyte membranes, contain any of the above-described solid glass electrolyte.
The invention also includes a kind of positive plates, coat the painting containing any description above composite positive pole on a current collector
Layer.
The invention also includes a kind of negative electrode tabs, and coating contains any description above composite negative pole material on a current collector.
The invention also includes a kind of all-solid-state supercapacitors, comprising by above-mentioned positive plate, negative electrode tab, solid glass electricity
Solve plasma membrane piece and diaphragm, and according to the positive plate, solid glass electrolyte membrane, diaphragm, solid glass electrolyte membrane, negative
The sequence of pole piece is laminated.
The invention also includes another all-solid-state supercapacitors, comprising by above-mentioned positive plate, negative electrode tab, solid glass
Electrolyte membrane, and be laminated according to the sequence of the positive plate, solid glass electrolyte membrane, negative electrode tab.
Solid electrolyte material conductivity with higher proposed by the present invention, meanwhile, supercapacitor production method will
Solid glass electrolyte precursor method directly positive or negative pole active material with closely merge, reach as liquid electrolyte
Conductive network.Meanwhile close double electrical layers are formed in positive and negative electrode active material and solid glass electrolyte two-phase interface,
Lithium ion diffusion and insertion, abjection ability are greatly improved, it is generally lower than liquid electrolyte to overcome solid electrolyte conductivity
Disadvantage has low internal resistance, to realize the high power characteristic of lithium ion all-solid-state supercapacitor.Technical feasibility of the invention
Property it is high, production stage is simple, can be used for being mass produced.
[Detailed description of the invention]
Fig. 1 is a kind of structural schematic diagram of all-solid-state supercapacitor.
Fig. 2 is all-solid-state supercapacitor another kind structural schematic diagram.
Fig. 3 is anode composite material enlarged diagram.
Fig. 4 is anode material enlarged diagram.
In figure: 1. plus plate current-collecting bodies, 2. anode composite materials, 3. solid electrolyte membranes, 4. negative current collectors, 5. cathode
Composite material, 6. diaphragms.
[specific embodiment]
Hereinafter, be described further with attached drawing for the present invention in conjunction with the embodiments, embodiment and attached drawing are only used for explaining
It is bright rather than limit the scope of protection of the present invention.
Embodiment 1
1. anode composite material is first made, by solid glass electrolyte precursor, including lithia (Li2O), barium monoxide
(BaO), lithium chloride (LiCl) is dried in a vacuum respectively, by Li2.99Ba0.005The stoichiometric ratio Li of OCl2O: BaO: LiCl=
In vacuum glove box be pre-mixed at 1: 0.005: 0.99, then, accounts for solid glass electrolysis according still further to solid glass electrolyte
Matter, carbon nanotube, active carbon three's material gross mass accounting 5% mix, wherein carbon nanotube: active carbon=1: 99,
Under argon atmosphere protection, said mixture is fitted into ball mill, zirconia ball is added, is fitted into sealing ball grinder, using row
Celestial body grinding machine carry out mechanical mixture, set Ball-milling Time 350rpm, every 30min stand 5min, ball milling mixing 15 hours, then
Under protection of argon gas by said mixture, it takes out from ball grinder, is sintered in vacuum tube furnace, heat treatment temperature
It is 235 DEG C, heat treatment time 20 hours, after heat treatment, is slowly cooled to room temperature, gained powder is solid electrolyte
Li2.99Ba0.005OCl and the compound active carbon positive electrode of carbon nanotube.
When making anode material, including lithia (Li2O), barium monoxide (BaO), lithium chloride (LiCl) is respectively true
It is aerial dry, by Li2.99Ba0.005The stoichiometric ratio Li of OCl2O: BaO: LiCl=1: 0.005: 0.99 in vacuum glove box
It is pre-mixed, then, accounts for solid glass electrolyte according still further to solid glass electrolyte, hard charcoal gross mass accounting 5% is mixed
It closes, under argon atmosphere protection, said mixture is fitted into ball mill, zirconia ball is added, be fitted into sealing ball grinder, adopt
Mechanical mixture is carried out with planetary ball mill, sets Ball-milling Time 350rpm, stands 5min every 30min, ball milling mixing 10 hours,
Then under protection of argon gas by said mixture, take out from ball grinder, be sintered in vacuum tube furnace, is heat-treated
Temperature is 230 DEG C, heat treatment time 20 hours, after heat treatment, is slowly cooled to room temperature, gained powder is solid electrolyte
Li2.99Ba0.005OCl composite negative pole hard carbon material.
2. under the inert atmosphere protections such as argon gas, by solid electrolyte Li2.99Ba0.005OCl and the compound work of carbon nanotube
Property charcoal positive electrode, binder PVDF mixed in 98:2 ratio, a certain amount of nmp solvent is added and stirs into slurry, it is then coated
Or the methods of printing is coated on foil and positive plate is made；
Under the inert atmosphere protections such as argon gas, by solid electrolyte Li2.99Ba0.005OCl composite negative pole hard carbon material with
PVDF is mixed in 98:2 ratio, and NMP is added and is mixed into slurry, and the methods of then coated or printing is coated in copper current collector
Upper obtained negative electrode tab；
3. by lithia (Li2O), barium monoxide (BaO), lithium chloride (LiCl) press Li2.99Ba0.005The stoichiometric ratio of OCl
Li2In vacuum glove box be pre-mixed at O: BaO: LiCl=1: 0.005: 0.99, will be above-mentioned mixed under argon atmosphere protection
It closes object to be fitted into ball mill, zirconia ball is added, be fitted into sealing ball grinder, mechanical mixture is carried out using planetary ball mill, if
Determine Ball-milling Time 300rpm, stands 5min every 30min, ball milling mixing 10 hours, then protect said mixture in argon gas
Under, it takes out from ball grinder, is sintered in vacuum tube furnace, heat treatment temperature is 230 DEG C, and heat treatment time 20 is small
When, it after heat treatment, is slowly cooled to room temperature, gained powder is solid glass electrolyte.By solid glass electrolyte powder
Body material makees solvent using NMP, is mixed into slurry, and uniformly after drying is dry, diaphragm is shelled on metal foil or glass for coating
From getting off to get to solid glass electrolyte membrane.
4. by the anode pole piece of above-mentioned preparation, solid glass electrolyte membrane, cellulosic separator, solid glass dielectric film
Piece, negative electrode tab stack gradually mode and are assembled into buckle type lithium-ion supercapacitor.Negative electrode tab use with lithium electrode short circuit manner into
Row prelithiation.Few drops of 1M LiPF are added dropwise on cellulosic separator6PC: DEC=1: 1 electrolyte, infiltrate cellulosic separator
Electrolyte.
Comparative example 2
1. traditionally making active carbon positive plate, active carbon positive electrode, binder PVDF are mixed in 98:2 ratio,
A certain amount of nmp solvent is added and stirs into slurry, the methods of then coated or printing is coated on foil and normal activated carbon is being made just
Pole piece；
Similarly, negative electrode tab is traditionally made, hard charcoal negative electrode material, binder PVDF are mixed in 98:2 ratio, added
Enter a certain amount of nmp solvent and stir into slurry, the methods of then coated or printing, which is coated on foil, is made common hard charcoal cathode living
Piece；
2. by lithia (Li2O), barium monoxide (BaO), lithium chloride (LiCl) press Li2.99Ba0.005The stoichiometric ratio of OCl
Li2In vacuum glove box be pre-mixed at O: BaO: LiCl=1: 0.005: 0.99, will be above-mentioned mixed under argon atmosphere protection
It closes object to be fitted into ball mill, zirconia ball is added, be fitted into sealing ball grinder, mechanical mixture is carried out using planetary ball mill, if
Determine Ball-milling Time 300rpm, stands 5min every 30min, ball milling mixing 10 hours, then protect said mixture in argon gas
Under, it takes out from ball grinder, is sintered in vacuum tube furnace, heat treatment temperature is 230 DEG C, and heat treatment time 20 is small
When, it after heat treatment, is slowly cooled to room temperature, gained powder is solid glass electrolyte.By solid glass electrolyte powder
Body material makees solvent using NMP, is mixed into slurry, and uniformly after drying is dry, diaphragm is shelled on metal foil or glass for coating
From getting off to get to solid glass electrolyte membrane.
3. the anode pole piece of above method preparation, solid glass electrolyte membrane, cellulosic separator, solid glass are electrolysed
Plasma membrane piece, cathode pole piece stack gradually mode and form buckle type lithium-ion supercapacitor, and are added dropwise on cellulosic separator few drops
PC: DEC=1: 1 electrolyte of 1M LiPF6 makes cellulosic separator infiltrate electrolyte.Negative electrode tab uses and lithium electrode short circuit side
Formula carries out prelithiation.
Embodiment 3
1. anode composite material is first made, by solid glass electrolyte precursor, including lithia (Li2O), barium hydroxide
(Ba(OH)2), lithium chloride (LiCl) is dried in a vacuum respectively, by Li2.98Ba0.01OCl1-x(OH)xThe change of (0≤x≤0.02)
It learns metering and compares Li2O∶Ba(OH)2: in vacuum glove box be pre-mixed at LiCl=1: 0.01: 0.99, then, according still further to solid-state
Vitreous electrolyte accounts for solid glass electrolyte, carbon nanotube, active carbon three's material gross mass accounting 5% and mixes, wherein
Carbon nanotube: active carbon=1: 99, under argon atmosphere protection, said mixture is fitted into ball mill, zirconia ball is added,
It is fitted into sealing ball grinder, mechanical mixture is carried out using planetary ball mill, sets Ball-milling Time 350rpm, is stood every 30min
5min ball milling mixing 15 hours, then under protection of argon gas by said mixture, takes out, in vacuum tube furnace from ball grinder
In be sintered, heat treatment temperature be 235 DEG C, heat treatment time 20 hours, after heat treatment, be slowly cooled to room temperature, institute
Obtaining powder is solid electrolyte Li2.98Ba0.01OCl1-x(OH)xThe active carbon positive electrode compound with carbon nanotube.
When making anode material, including lithia (Li2O), barium hydroxide (Ba (OH)2), lithium chloride (LiCl) is respectively
It is dried in a vacuum, by Li2.98Ba0.01OCl1-x(OH)xStoichiometric ratio Li2O∶Ba(OH)2: LiCl=1: 0.01: 0.99
It is pre-mixed in vacuum glove box, then, accounts for solid glass electrolyte according still further to solid glass electrolyte, hard charcoal gross mass accounts for
It is mixed than 5%, under argon atmosphere protection, said mixture is fitted into ball mill, zirconia ball is added, is packed into sealing
In ball grinder, mechanical mixture is carried out using planetary ball mill, sets Ball-milling Time 350rpm, stands 5min, ball milling every 30min
Mixing 10 hours, then under protection of argon gas by said mixture, takes out from ball grinder, is sintered in vacuum tube furnace
Processing, heat treatment temperature are 230 DEG C, heat treatment time 20 hours, after heat treatment, are slowly cooled to room temperature, gained powder is
Solid electrolyte Li2.98Ba0.01OCl1-x(OH)xComposite negative pole hard carbon material.
2. under the inert atmosphere protections such as argon gas, by solid electrolyte Li2.98Ba0.01OCl1-x(OH)xIt is multiple with carbon nanotube
Active carbon positive electrode, the binder PVDF of conjunction are mixed in 98:2 ratio, and a certain amount of nmp solvent is added and stirs into slurry, then
The methods of coated or printing, which is coated on foil, is made positive plate；
Under the inert atmosphere protections such as argon gas, by solid electrolyte Li2.98Ba0.01OCl1-x(OH)xComposite negative pole hard charcoal material
Material is mixed with PVDF in 98:2 ratio, and NMP is added and is mixed into slurry, and the methods of then coated or printing is coated in copper collection
Negative electrode tab is made on fluid；
3. by lithia (Li2O), barium hydroxide (Ba (OH)2), lithium chloride (LiCl) presses Li2.98Ba0.01OCl1-x(OH)x's
Stoichiometric ratio Li2O∶Ba(OH)2: in vacuum glove box be pre-mixed at LiCl=1: 0.01: 0.99, is protected in argon atmosphere
Under shield, said mixture is fitted into ball mill, be added zirconia ball, is fitted into seal ball grinder in, using planetary ball mill into
Row mechanical mixture, set Ball-milling Time 300rpm, every 30min stand 5min, ball milling mixing 10 hours, then by above-mentioned mixing
Object under protection of argon gas, takes out from ball grinder, is sintered in vacuum tube furnace, and heat treatment temperature is 230 DEG C, heat
The processing time 20 hours, after heat treatment, is slowly cooled to room temperature, gained powder is solid glass electrolyte.By solid-state
Vitreous electrolyte powder body material makees solvent using NMP, is mixed into slurry, and uniformly on metal foil or glass, drying is dry for coating
After dry to get arrive solid glass electrolyte Li2.98Ba0.01OCl1-x(OH)xDiaphragm.
4. by anode pole piece, solid glass electrolyte membrane, cellulosic separator, solid glass electrolyte membrane, negative electrode tab
The mode of stacking gradually forms battery core, then uses aluminum plastic film material package Soft Roll type lithium ion super capacitor.Aforementioned cellulose
Diaphragm is handled by electrolyte-impregnated, and solid glass electrolyte is used nmp solvent, stirs into dispersion liquid, diaphragm is impregnated in
It states in dispersion liquid and is dried to obtain containing Li2.98Ba0.01OCl1-x(OH)xCellulosic separator.Negative electrode tab uses and lithium electrode short circuit side
Formula carries out prelithiation.
Embodiment 4
1. traditionally making active carbon positive plate, active carbon positive electrode, binder PVDF are mixed in 98:2 ratio,
A certain amount of nmp solvent is added and stirs into slurry, the methods of then coated or printing is coated on foil and normal activated carbon is being made just
Pole piece；
Similarly, negative electrode tab is traditionally made, hard charcoal negative electrode material, binder PVDF are mixed in 98:2 ratio, added
Enter a certain amount of nmp solvent and stir into slurry, the methods of then coated or printing, which is coated on foil, is made common hard charcoal cathode living
Piece；
2. by lithia (Li2O), barium hydroxide (Ba (OH)2), lithium chloride (LiCl) presses Li2.98Ba0.01OCl1-x(OH)x(0
≤ x≤0.02) stoichiometric ratio Li2O∶Ba(OH)2: in vacuum glove box be pre-mixed at LiCl=1: 0.01: 0.99,
Under argon atmosphere protection, said mixture is fitted into ball mill, zirconia ball is added, is fitted into sealing ball grinder, uses
Planetary ball mill carry out mechanical mixture, set Ball-milling Time 300rpm, every 30min stand 5min, ball milling mixing 10 hours, so
Afterwards under protection of argon gas by said mixture, it takes out from ball grinder, is sintered in vacuum tube furnace, heat treatment temperature
Degree is 230 DEG C, heat treatment time 20 hours, after heat treatment, is slowly cooled to room temperature, gained powder is solid glass electrolyte
Material.Solid glass electrolyte powder material is made into solvent using NMP, is mixed into slurry, uniformly coating and metal foil or glass
On glass, after drying is dry, diaphragm is stripped down to get solid glass electrolyte Li is arrived2.98Ba0.01OCl1-x(OH)xDiaphragm.
3. by above-mentioned common anode pole piece, solid glass electrolyte membrane, cellulosic separator, solid glass dielectric film
Piece, common negative electrode tab stack gradually mode and form Soft Roll lithium ion super capacitor.Aforementioned cellulosic separator is soaked by electrolyte
Solid glass electrolyte is used nmp solvent, stirs into dispersion liquid, diaphragm is impregnated in above-mentioned dispersion fluid drying and obtains by stain processing
To containing Li2.98Ba0.01OCl1-x(OH)xCellulosic separator, negative electrode tab, which is used, carries out prelithiation with lithium electrode short circuit manner.
Embodiment 5
1. anode composite material is first made, by solid glass electrolyte precursor, including lithium sulfide (Li2S), lithium carbonate
(Li2CO3), lithium iodide (LiI) be dried in a vacuum respectively, by Li2.98SI1-x(CO3)xThe stoichiometric ratio of (0≤x≤0.02)
Li2S∶Li2CO3: in vacuum glove box be pre-mixed at LiI=1: 0.02: 0.98, then, according still further to solid glass electrolyte
It accounts for solid glass electrolyte, carbon nanotube, active carbon three's material gross mass accounting 10% to mix, wherein carbon nanotube:
Active carbon=5: 85, under argon atmosphere protection, said mixture is fitted into ball mill, zirconia ball is added, is packed into sealing
In ball grinder, mechanical mixture is carried out using planetary ball mill, sets Ball-milling Time 350rpm, stands 5min, ball milling every 30min
Mixing 15 hours, then under protection of argon gas by said mixture, takes out from ball grinder, is sintered in vacuum tube furnace
Processing, heat treatment temperature are 235 DEG C, heat treatment time 20 hours, after heat treatment, are slowly cooled to room temperature, gained powder is
Solid electrolyte Li2.98SI1-x(CO3)xThe active carbon positive electrode compound with carbon nanotube.
When making anode material, including lithium sulfide (Li2S), lithium carbonate (Li2CO3), lithium iodide (LiI) is respectively true
It is aerial dry, by Li2.98SI1-x(CO3)xStoichiometric ratio Li2S∶Li2CO3: LiI=1: 0.02: 0.98 in vacuum glove box
In be pre-mixed, then, according still further to solid glass electrolyte account for solid glass electrolyte, hard charcoal gross mass accounting 10% carry out
Said mixture is fitted into ball mill by mixing under argon atmosphere protection, and zirconia ball is added, and is fitted into sealing ball grinder,
Mechanical mixture is carried out using planetary ball mill, sets Ball-milling Time 350rpm, stands 5min every 30min, ball milling mixing 10 is small
When, it then under protection of argon gas by said mixture, takes out from ball grinder, is sintered in vacuum tube furnace, heat
Treatment temperature is 230 DEG C, heat treatment time 20 hours, after heat treatment, is slowly cooled to room temperature, gained powder is solid electrolytic
Matter Li2.98SI1-x(CO3)xComposite negative pole hard carbon material.
2. under the inert atmosphere protections such as argon gas, by solid electrolyte Li2.98SI1-x(CO3)xThe compound work with carbon nanotube
Property charcoal positive electrode, binder PVDF mixed in 98:2 ratio, a certain amount of nmp solvent is added and stirs into slurry, it is then coated
Or the methods of printing is coated on foil and positive plate is made；
Under the inert atmosphere protections such as argon gas, by solid electrolyte Li2.98SI1-x(CO3)xComposite negative pole hard carbon material with
PVDF is mixed in 98:2 ratio, and NMP is added and is mixed into slurry, and the methods of then coated or printing is coated in copper current collector
Upper obtained negative electrode tab；
3. by lithium sulfide (Li2S), lithium carbonate (Li2CO3), lithium iodide (LiI) be dried in a vacuum respectively, press
Li2.98SI1-x(CO3)xStoichiometric ratio Li2S∶Li2CO3: in vacuum glove box premixed at LiI=1: 0.02: 0.98
It closes, under argon atmosphere protection, said mixture is fitted into ball mill, zirconia ball is added, be fitted into sealing ball grinder, adopt
Mechanical mixture is carried out with planetary ball mill, sets Ball-milling Time 300rpm, stands 5min every 30min, ball milling mixing 10 hours,
Then under protection of argon gas by said mixture, take out from ball grinder, be sintered in vacuum tube furnace, is heat-treated
Temperature is 230 DEG C, heat treatment time 20 hours, after heat treatment, is slowly cooled to room temperature, and gained powder is solid glass electrolysis
Material.Solid glass electrolyte powder material is made into solvent using NMP, is mixed into slurry, uniformly coating and metal foil or
On glass, after drying is dry, diaphragm is stripped down and obtains solid glass electrolyte Li2.98SI1-x(CO3)xDiaphragm.
Surpass 4. anode pole piece, solid glass electrolyte membrane, negative electrode tab are stacked gradually mode and form Soft Roll type lithium ion
Grade capacitor, negative electrode tab, which is used, carries out prelithiation with lithium electrode short circuit manner, and all-solid-state supercapacitor is made.
Embodiment 6
Positive plate, negative electrode tab, the manufacturing process of solid glass electrolyte membrane are same as Example 5 in embodiment 6, for into
One step compares, and the assembling mode of lithium ion super capacitor carries out in the following manner in the present embodiment.
By above-mentioned common anode pole piece, solid glass electrolyte membrane, cellulosic separator, solid glass electrolyte membrane,
Common negative electrode tab stacks gradually mode and forms Soft Roll type lithium ion super capacitor.Aforementioned cellulosic separator passes through electrolyte-impregnated
Processing, by solid glass electrolyte Li2.98SI1-x(CO3)xUsing nmp solvent, dispersion liquid is stirred into, diaphragm is impregnated in above-mentioned point
It is dried to obtain in dispersion liquid containing Li2.98SI1-x(CO3)xCellulosic separator, negative electrode tab, which is used, carries out pre- lithium with lithium electrode short circuit manner
Change.
Embodiment 7
1. anode composite material is first made, by solid glass electrolyte precursor, including lithium sulfide (Li2S), lanthanum nitrate
(La(NO3)2), lithium bromide (LiBr) be dried in a vacuum respectively, by Li2.725La0.1375SBr1-x(NO3)x(0≤x≤0.275)
Stoichiometric ratio Li2S∶La(NO3)2: in vacuum glove box be pre-mixed at LiBr=1: 0.1375: 0.725, then, then
Solid glass electrolyte, carbon nanotube, active carbon three's material gross mass accounting 10% is accounted for according to solid glass electrolyte to carry out
It mixes, wherein carbon nanotube: active carbon=5: 85, under argon atmosphere protection, said mixture is fitted into ball mill, is added
Zirconia ball, is fitted into sealing ball grinder, carries out mechanical mixture using planetary ball mill, sets Ball-milling Time 350rpm, every
30min stands 5min, ball milling mixing 15 hours, then under protection of argon gas by said mixture, takes out from ball grinder, true
It is sintered in empty tube furnace, heat treatment temperature is 235 DEG C, heat treatment time 20 hours, after heat treatment, is slowly cooled to
Room temperature, gained powder are solid electrolyte Li2.725La0.1375SBr1-x(NO3)xThe active carbon anode material compound with carbon nanotube
Material.
When making anode material, including lithium sulfide (Li2S), lanthanum nitrate (La (NO3)2), lithium bromide (LiBr) respectively
It is dried in a vacuum, by Li2.725La0.1375SBr1-x(NO3)xStoichiometric ratio Li2S∶La(NO3)2: LiBr=1: 0.1375:
0.725 is pre-mixed in vacuum glove box, then, accounts for solid glass electrolyte, hard charcoal according still further to solid glass electrolyte
Gross mass accounting 10% is mixed, and under argon atmosphere protection, said mixture is fitted into ball mill, zirconium oxide is added
Ball, is fitted into sealing ball grinder, carries out mechanical mixture using planetary ball mill, sets Ball-milling Time 350rpm, quiet every 30min
5min is set, ball milling mixing 10 hours, then under protection of argon gas by said mixture, is taken out from ball grinder, in electron tubes type
It being sintered in furnace, heat treatment temperature is 230 DEG C, it heat treatment time 20 hours, after heat treatment, is slowly cooled to room temperature,
Gained powder is solid electrolyte Li2.725La0.1375SBr1-x(NO3)xComposite negative pole hard carbon material.
2. under the inert atmosphere protections such as argon gas, by solid electrolyte Li2.725La0.1375SBr1-x(NO3)xAnd carbon nanotube
Compound active carbon positive electrode, binder PVDF are mixed in 98:2 ratio, and a certain amount of nmp solvent is added and stirs into slurry, so
It is coated on foil by the methods of coating or printing and positive plate is made；
Under the inert atmosphere protections such as argon gas, by solid electrolyte Li2.725La0.1375SBr1-x(NO3)xComposite negative pole hard charcoal
Material and PVDF are mixed in 98:2 ratio, and NMP is added and is mixed into slurry, and the methods of then coated or printing is coated in copper
Negative electrode tab is made on collector；
3. by solid glass electrolyte precursor, including lithium sulfide (Li2S), lanthanum nitrate (La (NO3)2), lithium bromide
(LiBr) it is dried in a vacuum respectively, by Li2.725La0.1375SBr1-x(NO3)xStoichiometric ratio Li2S∶Li2CO3: LiI=1:
In vacuum glove box be pre-mixed at 0.02: 0.98, and under argon atmosphere protection, said mixture is fitted into ball mill,
Zirconia ball is added, is fitted into sealing ball grinder, mechanical mixture is carried out using planetary ball mill, sets Ball-milling Time 300rpm,
5min is stood every 30min, ball milling mixing 10 hours, then under protection of argon gas by said mixture, is taken out from ball grinder,
It is sintered in vacuum tube furnace, heat treatment temperature is 230 DEG C, heat treatment time 20 hours, slowly cold after heat treatment
But to room temperature, gained powder is solid glass electrolyte.NMP is used to do solid glass electrolyte powder material molten
Agent is mixed into slurry, and uniformly coating arrives solid glass electrolyte after drying is dry on metal foil or glass
Li2.725La0.1375SBr1-x(NO3)xDiaphragm.
It is fitted into button shell, compresses 4. anode pole piece, solid glass electrolyte membrane, negative electrode tab are stacked gradually, bear
Pole piece, which is used, carries out prelithiation with lithium electrode short circuit manner, and all-solid-state supercapacitor is made.
Embodiment 8
Further to be compared with embodiment 7, positive plate, solid glass electrolyte membrane, negative electrode tab production method
It is same as Example 7, diaphragm only is removed in the assembling process of lithium ion super capacitor, is compared in solid glass electrolyte
The function and effect of diaphragm substitution diaphragm.
It is fitted into button shell, compresses 4. anode pole piece, solid glass electrolyte membrane, negative electrode tab are stacked gradually, bear
Pole piece, which is used, carries out prelithiation with lithium electrode short circuit manner, and all-solid-state supercapacitor is made.
Embodiment 9
1. anode composite material is first made, by solid glass electrolyte precursor, including lithium sulfide (Li2S), lithia
(Li2O), barium chlorate (Ba (ClO3)2), lithium chloride (LiCl) be dried in a vacuum respectively, by Li2.6Ba0.2SCl1-x(ClO3)x(0
≤ x≤0.4) stoichiometric ratio Li2S∶Ba(ClO3)2: in vacuum glove box be pre-mixed at LiCl=1: 0.2: 0.6, so
Afterwards, solid glass electrolyte, carbon nanotube, active carbon three's material gross mass accounting 10% are accounted for according still further to solid glass electrolyte
It is mixed, wherein carbon nanotube: active carbon=5: 85, under argon atmosphere protection, said mixture is fitted into ball mill,
Zirconia ball is added, is fitted into sealing ball grinder, mechanical mixture is carried out using planetary ball mill, sets Ball-milling Time 350rpm,
5min is stood every 30min, ball milling mixing 15 hours, then under protection of argon gas by said mixture, is taken out from ball grinder,
It is sintered in vacuum tube furnace, heat treatment temperature is 235 DEG C, heat treatment time 20 hours, slowly cold after heat treatment
But to room temperature, gained powder is solid electrolyte Li2.6Ba0.2SCl1-x(ClO3)xThe compound active carbon anode with carbon nanotube
Material.
When making anode material, including lithium sulfide (Li2S), lithia (Li2O), barium chlorate (Ba (ClO3)2), chlorine
Change lithium (LiCl) to be dried in a vacuum respectively, by by Li2.6Ba0.2SCl1-x(ClO3)xStoichiometric ratio Li2S∶Ba(ClO3)2∶
In vacuum glove box be pre-mixed at LiCl=1: 0.2: 0.6, then, accounts for solid glass electricity according still further to solid glass electrolyte
Xie Zhi, hard charcoal gross mass accounting 10% are mixed, and under argon atmosphere protection, said mixture are fitted into ball mill, is added
Enter zirconia ball, be fitted into sealing ball grinder, mechanical mixture is carried out using planetary ball mill, sets Ball-milling Time 350rpm, often
5min is stood every 30min, ball milling mixing 10 hours, then under protection of argon gas by said mixture, is taken out from ball grinder,
Be sintered in vacuum tube furnace, heat treatment temperature be 230 DEG C, heat treatment time 20 hours, after heat treatment, Slow cooling
To room temperature, gained powder is solid electrolyte Li2.6Ba0.2SCl1-x(ClO3)xComposite negative pole hard carbon material.
2. under the inert atmosphere protections such as argon gas, by solid electrolyte Li2.6Ba0.2SCl1-x(ClO3)xIt is multiple with carbon nanotube
Active carbon positive electrode, the binder PVDF of conjunction are mixed in 98:2 ratio, and a certain amount of nmp solvent is added and stirs into slurry, then
The methods of coated or printing, which is coated on foil, is made positive plate；
Under the inert atmosphere protections such as argon gas, by solid electrolyte Li2.6Ba0.2SCl1-x(ClO3)xComposite negative pole hard charcoal material
Material is mixed with PVDF in 98:2 ratio, and NMP is added and is mixed into slurry, and the methods of then coated or printing is coated in copper collection
Negative electrode tab is made on fluid；
3. by solid glass electrolyte precursor, including including lithium sulfide (Li2S), lithia (Li2O), barium chlorate (Ba
(ClO3)2), lithium chloride (LiCl) be dried in a vacuum respectively, by Li2.6Ba0.2SCl1-x(ClO3)xStoichiometric ratio Li2S∶Ba
(ClO3)2: in vacuum glove box be pre-mixed at LiCl=1: 0.2: 0.6, under argon atmosphere protection, by said mixture
It is fitted into ball mill, zirconia ball is added, be fitted into sealing ball grinder, mechanical mixture is carried out using planetary ball mill, sets ball
Consume time 300rpm, every 30min stand 5min, ball milling mixing 10 hours, then under protection of argon gas by said mixture, from
It takes out in ball grinder, is sintered in vacuum tube furnace, heat treatment temperature is 230 DEG C, heat treatment time 20 hours, hot
It after processing, is slowly cooled to room temperature, gained powder is solid glass electrolyte.By solid glass electrolyte powder material
Solvent is done using NMP, is mixed into slurry, uniformly coating arrives solid glass after drying is dry on metal foil or glass
Electrolyte Li2.6Ba0.2SCl1-x(ClO3)xDiaphragm.
It is fitted into button shell, compresses 4. anode pole piece, solid glass electrolyte membrane, negative electrode tab are stacked gradually, bear
Pole piece, which is used, carries out prelithiation with lithium electrode short circuit manner, and all-solid-state supercapacitor is made.
The above method prepares lithium ion super capacitor and is tested for the property.Specific performance index is shown in Table 1.
The comparison of 1 embodiment diaphragm properties of sample index of table
Claims (15)
1. a kind of solid glass electrolyte, it is characterised in that its chemical formula is Li3+x-2yMyA1+z-wB1+x-2z-2w ,
Wherein:
M chemical valence is+2, be it is a kind of in Mg, Ca, Sr, Ba, Ge, La, Ti, Zr, Zn, Ni element, A chemical valence is -2, be O, S or
One of Se,
B chemical valence is -1, is one of F, Cl, Br or I,
0 < x≤1,0≤y≤0.1,0≤z < 1,0≤w < 1, and w≤x.
2. a kind of solid glass electrolyte, it is characterised in that its chemical formula is Li3+x-2yMyA1+z-wB1+x-2z-2w-nbDb ,
Wherein:
M chemical valence is+2, be it is a kind of in Mg, Ca, Sr, Ba, Ge, La, Ti, Zr, Zn, Ni element, A chemical valence is -2, be O, S or
One of Se,
B chemical valence is -1, is one of F, Cl, Br or I,
D chemical valence is-n, is selected from OH-、PF6 -、BF4 -、CO3 2-、CF3SO3 -、CH3 -、CH3CO2 -、ClO2 -、ClO3 -、ClO4 -、H2PO4 -、
HCO3 -、HF2 -、HSO4 -、IO3 -、IO4 -、NH2 -、NH2CH2COO-、NO3 -、PO3 -、S6 -、SCN-、B(OH)4 -、SO3F-And N3-In
It is one or more,
0 < x≤1,0≤y≤0.1,0≤z < 1,0≤w < 1, and w≤x, 0≤b < 1, and b≤(2z-2w- x)/
n。
3. a kind of composite positive pole, including positive active material particle, it is characterised in that in positive active material particle surface
Be compounded with any solid glass electrolyte of claim 1 ~ 2, it is described it is compound be the solid glass electrolyte forerunner
Body is directly formed after vacuum heat treatment between 200 DEG C ~ 500 DEG C together with positive active material particle.
4. composite positive pole as claimed in claim 2, it is characterised in that further include conductive agent.
5. composite positive pole as claimed in claim 2, it is characterised in that the solid glass electrolyte accounts for anode composite material
Expect the 2 ~ 60% of total weight.
6. a kind of composite negative pole material, including anode active material particles, it is characterised in that on anode active material particles surface
Be compounded with any solid glass electrolyte of claim 1 ~ 4, it is described it is compound be the solid glass electrolyte forerunner
Body is directly formed after vacuum heat treatment between 200 DEG C ~ 500 DEG C together with anode active material particles.
7. composite negative pole material as claimed in claim 6, it is characterised in that further include conductive agent.
8. composite negative pole material as claimed in claim 6, it is characterised in that the solid glass electrolyte accounts for composite negative pole material
Expect the 2 ~ 60% of total weight.
9. a kind of preparation method of composite positive pole, it is characterised in that any solid glass electrolyte of claim 1 ~ 2
Presoma be formed directly into positive-active after vacuum heat treatment between 200 DEG C ~ 500 DEG C together with positive active material particle
Material grains surface.
10. a kind of preparation method of composite negative pole material, it is characterised in that any solid glass electrolyte of claim 1 ~ 2
Presoma be formed directly into negative electrode active after vacuum heat treatment between 200 DEG C ~ 500 DEG C together with anode active material particles
Material grains surface.
11. a kind of solid glass electrolyte membrane, it is characterised in that contain any solid glass electrolysis of claim 1 ~ 2
Matter.
12. a kind of positive plate, it is characterised in that coating contains any composite positive pole of claim 3 ~ 5 on a current collector
Coating.
13. a kind of negative electrode tab, it is characterised in that coating contains any composite negative pole material of claim 6 ~ 8 on a current collector
Material.
14. a kind of all-solid-state supercapacitor, it is characterised in that include positive plate, claim 13 as described in claim 12
Solid glass electrolyte membrane and diaphragm described in the negative electrode tab, claim 11, and according to the positive plate, solid-state glass
The sequence stacking of glass electrolyte membrane, diaphragm, solid glass electrolyte membrane, negative electrode tab.
15. a kind of all-solid-state supercapacitor, it is characterised in that include positive plate, claim 13 as described in claim 12
Solid glass electrolyte membrane described in the negative electrode tab, claim 11, and be electrolysed according to the positive plate, solid glass
The sequence stacking of plasma membrane piece, negative electrode tab.
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