CN110350238A - A kind of all-solid lithium-ion battery and preparation method thereof with porous gradient-structure - Google Patents
A kind of all-solid lithium-ion battery and preparation method thereof with porous gradient-structure Download PDFInfo
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Abstract
The all-solid lithium-ion battery and preparation method thereof with porous gradient-structure that this application involves a kind of.The all-solid lithium-ion battery, it include: the anode pole piece with composite positive pole layer, the cathode pole piece with composite negative pole material layer and the solid electrolyte between the anode pole piece and the cathode pole piece, it is characterized by: the composite positive pole layer has micropore, and the porosity of micropore is successively decreased in the vertical direction away from plus plate current-collecting body；There is micropore with the composite negative pole material layer, and the porosity of micropore is successively decreased in the vertical direction away from negative current collector, wherein the micropore is at least partly filled by solid electrolyte.The interface impedance of solid electrolyte and electrode material is significantly reduced by the electrode structural designs of porous gradient-structure, it ensures that the active material in battery in solid electrolyte and positive and negative anodes forms effective and controllable contact area simultaneously, therefore there is high high rate performance and cycle performance.
Description
Technical field
The present invention relates to all-solid-state battery field more particularly to a kind of all solid state lithium ion electricity with porous gradient-structure
Pond and preparation method thereof.
Background technique
Solid lithium ion battery mainly use solid electrolyte material replace conventional lithium ion battery in electrolyte and every
The effect of film, this not only simplifies battery structures, simultaneously because the performances such as incombustibility of solid electrolyte material, improve lithium
The safety of ion battery, while avoiding the safety problems such as electrolyte leakage.Therefore, solid lithium ion battery has wide
Application prospect.
However, the commercial applications of current solid lithium ion battery still suffer from many difficult points, for example, solid electrolyte with
Electrode material have high interface impedance, solid electrolyte material processing performance there is still a need for improve, simple possible it is extensive
Production technology also needs to constantly improve.In order to which solid lithium ion battery is accomplished mass production, select suitable technique will
Solid electrolyte material is made into slurry and optimizes the boundary of solid electrolyte and electrode material by the design of positive and negative anodes structure
Face impedance is most important.
Chinese patent application 201110344937.7 discloses a kind of all-solid-state battery, which uses a kind of gradient knot
Structure, the anode (cathode) of the battery in gradient, are showed containing the volume ratio of positive (cathode) active material and solid electrolyte:
It is relatively high close to anode (cathode) active material on anode (cathode) afflux side and the volume of solid electrolyte, close to solid electricity
The volume of anode (cathode) active material and solid electrolyte that solve matter layer is relatively low.Meanwhile the anode (cathode) of the battery
Voidage has gradient, and direction is to be gradually reduced from collector side to solid electrolyte layer direction.
However, expansion and contraction when although the gap in this battery structure can absorb battery charging and discharging, will affect
" flowing " of lithium in the electrolyte.Simultaneously as the porous structure of active material layer, has with the unit of solid electrolyte material
Effect releasing area is less, can not constitute effective conductive network, therefore, interface impedance is higher.
Therefore, it is necessary to a kind of reduced interface impedance and all solid state lithium ion of the solid electrolyte contact area of increase electricity
Pond.
Summary of the invention
In view of this, the main purpose of the present invention is to provide a kind of solid lithium ion batteries with porous gradient-structure
And preparation method thereof, by utilizing the tape casting after mixing positive and negative anodes active material, conductive agent, dispersing agent, pore creating material, plasticizer
Prepare the electrode material with porous gradient-structure.
In order to achieve the above objectives, technical solution of the present invention is realized by following scheme:
The first aspect of the present invention provides a kind of all-solid lithium-ion battery, comprising:
Anode pole piece with composite positive pole layer, the cathode pole piece with composite negative pole material layer and be located at it is described just
Solid electrolyte between pole pole piece and the cathode pole piece, it is characterised in that:
The composite positive pole layer has micropore, and the porosity of micropore is in the vertical direction away from plus plate current-collecting body
Successively decrease；With
The composite negative pole material layer has micropore, and the porosity of micropore is in the vertical direction away from negative current collector
Successively decrease,
Wherein, the micropore is at least partly filled by solid electrolyte.
According to one embodiment, the overall porosity of the micropore is 5%~20%, and the aperture of the micropore is 5~15 μ
m。
According to one embodiment, the solid electrolyte is in the composite positive pole layer and the composite negative pole material
It is in net distribution in layer.
According to one embodiment, the micropore is formed by the pore creating material of content distribution gradient, based on it is described it is compound just
The gross mass of pole material layer, total amount of the pore creating material in the composite positive pole layer are 2~10wt%, and based on described
The gross mass of composite negative pole material layer, total amount of the pore creating material in the composite negative pole material layer are 2~10wt%.
Further, the pore creating material be selected from poly (methyl methacrylate) micro-sphere (PMMA), starch, carbon dust, ammonium hydrogen carbonate,
One of PS microballoon is a variety of, wherein the partial size of the pore creating material is 5~15 μm.
According to one embodiment, the composite positive pole layer is made of m layers of sub-layer, wherein micropore in i-th layer of sub-layer
Porosity gradually successively decreased by the 1st layer adjacent with plus plate current-collecting body, wherein m be 2~10 integer, i be 1~m integer；And
The composite negative pole material layer is made of n-layer sub-layer, wherein the porosity of micropore is by adjacent with negative current collector in jth sub-layer
The 1st layer gradually successively decrease, wherein n be 2~10 integer, j be 1~n integer.
Further, the sub-layer with a thickness of 10~80 μm.
The second aspect of the present invention provides all-solid lithium-ion battery described in preparation first aspect present invention, comprising:
The pore creating material of different content is mixed to get anode composite sub-layer with composite positive pole respectively, and presses the pore-creating
The sequence that the content of agent is successively decreased in the vertical direction away from plus plate current-collecting body is successively laminated the anode composite sub-layer,
Then pore creating material is made to form the micropore；
The pore creating material of different content is mixed to get composite negative pole sub-layer with composite negative pole material respectively, and presses the pore-creating
The sequence that the content of agent is successively decreased in the vertical direction away from plus plate current-collecting body is successively laminated the composite negative pole sub-layer,
Then pore creating material is made to form the micropore；
Wherein, the micropore is filled using solid electrolyte.
According to one embodiment, the pore creating material of m group different content is mixed to form m layers again with composite positive pole respectively
Close positive sub-layer, wherein the integer that m is 2~10, and
The pore creating material of n group different content is mixed to form n-layer anode composite sub-layer with composite positive pole respectively, wherein n
For 2~10 integer.
According to one embodiment, temperature, the vacuum of -20~-100Kpa of the pore creating material at 500 DEG C~850 DEG C
Degree is lower to carry out vacuum-sintering to form the micropore.
It according to one embodiment, is that will be formed with the lamination leaching of micropore with the mode that solid electrolyte fills the micropore
Stain is in the slurry of solid electrolyte.
The beneficial effects of the present invention are significantly reduce solid electricity by the electrode structural designs of porous gradient-structure
The interface impedance of Xie Zhiyu electrode material, meanwhile, the battery of this structure ensures in battery in solid electrolyte and positive and negative anodes
Active material form effective and controllable contact area, therefore there is high high rate performance and cycle performance.
Detailed description of the invention
Fig. 1 is the schematic diagram of the porous gradient-structure all-solid lithium-ion battery of the present invention；
Fig. 2 is the surface topography micro-structure diagram of the anode composite pole piece of the porous gradient-structure of the present invention；
Fig. 3 is the interface impedance comparison of all-solid-state battery prepared by comparative example 1 and all-solid-state battery prepared by embodiment 1
Figure；With
Fig. 4 is the cycle performance comparison of all-solid-state battery prepared by comparative example 1 and all-solid-state battery prepared by embodiment 1
Figure.
Specific embodiment
Hereinafter, will be described in detail with reference to accompanying drawings solid lithium ion battery according to the present invention and preparation method thereof.The present invention
Solid lithium ion battery be made of anode pole piece, solid electrolyte and cathode pole piece, wherein in anode pole piece and cathode pole piece
Containing the solid electrolyte of Graded amounts.
Anode pole piece and cathode pole piece containing gradient solid electrolyte are prepared as follows.
1, solid electrolyte layer is prepared
Solid electrolyte layer 301 is made of solid electrolyte, it is necessary first to which the slurry for preparing solid electrolyte is subsequently coated with
Solid electrolyte is obtained after being allowed to solidification on to carrier, is finally detached from the carrier to obtain solid electrolyte layer 301.
Solid electrolyte slurry of the present invention, comprising: solid electrolyte powder, solvent, binder.
Specifically, the solid electrolyte powder in solid electrolyte slurry of the present invention is Li7La3Zr2O12(LLZO)、
Li10GeP2S12(LGPS)、Li1+xAlxTi2-x(PO4)3(LATP, x=0~0.4), Li1+xAlxGe2-x(PO4)3(LAGP, x=0~
0.75)、Li0.5-3xLa0.5+xTiO3(LLTO, x=0~0.8), xLi2S-yP2S5(x+y=100) and Li6PS5Group composed by X
At least one of, wherein X Cl, Br or I.
Wherein, the average grain diameter of solid electrolyte powder is 100~500nm, preferably 100~150nm.
Solvent in solid electrolyte slurry of the present invention is water (H2O), methanol (CH3OH), ethyl alcohol (C2H6O), heptane
(C7H16), toluene (C7H8), dimethylbenzene (C8H10), butyl butyrate (C8H16O2), N-Methyl pyrrolidone (C5H9NO), methyl tert-butyl
Base ketone (C6H12O), nitrile (C2N3H), tetrahydrofuran (C4H8O), ether (C4H10One or more of O).
Wherein, the additive amount of solvent is preferably 10wt%~35wt% of powder gross mass.
Binder in solid electrolyte slurry of the present invention is SBR, PVDF, PVDF-HFP, PVB, silica gel, SBS,
One or more of PEG.
Wherein, the additive amount of binder is preferably 1wt%~15wt%.
Solid electrolyte slurry preparation method includes the following steps:
(1) stand-by solid electrolyte powder, binder powder are placed in drying box and are dried 12h, dry temperature
Degree is 60 DEG C~150 DEG C；
(2) solid electrolyte powder, binder are weighed in proportion and is placed in ball mill container, then proportionally in ball
Solvent is added in mill container, ball mill container is sealed after processing at 30 DEG C~80 DEG C by 100r/min~800r/min's
Revolving speed ball milling 3h~12h obtains uniformly mixed solid electrolyte slurry；
It after obtaining solid electrolyte slurry, needs to be coated on carrier, which is usually rigid sheet, such as aluminium
Foil, copper foil, nickel foil, stainless steel, on electroconductive resin, it is then separated and form solid electrolyte layer 301.
Therefore, the preparation method of solid electrolyte layer further includes following steps:
The mixed uniformly solid electrolyte slurry that above-mentioned steps (2) ball milling is prepared is poured on foil (not shown)
On, the spacing of scraper and foil is then adjusted to 10~35 μm and carries out coating process, the solid electrolytic that coating is completed
Matter pole piece is transferred to vacuum oven and dry 10~for 24 hours, and drying temperature is 45~85 DEG C, and vacuum degree is -40~-
100Kpa obtains solid electrolyte layer 301.
The then carrier plate in removing solid electrolyte layer, obtains solid electrolyte layer 301.
2, the composite positive pole layer of the solid electrolyte containing gradient is prepared
There is the anode composite layer 102 of porous gradient firstly the need of preparation, for this purpose, what the present invention used answers
It closes anode layer 102 and needs to be divided into multiple sub-layers, the pore creating material of different content is wherein used in these sub-layers, is made in each sub-layer
Content of Pore-forming Agents is more, and the quantity of the micropore subsequently formed is also more.Therefore Graded amounts are used in these sub-layers
Pore creating material, the positive electrode material layer being made of these sub-layers just has the pore creating material of Graded amounts, after shaping, these pore creating materials
Hole is formed after decomposition, obtains the anode composite layer 102 with porous gradient, and pore creating material stays after high temperature sintering volatilization is decomposed
The hole of lower same size.
That is: the 1st layer of composite positive pole layer sub-layer is prepared, wherein first with the content meter of the 1st layer of sub-layer, the 1st layer of sub-layer
Content comprising pore creating material is a1,；
Prepare the 2nd layer of sub-layer, wherein with the content meter of the 1st layer of sub-layer, the 2nd layer of sub-layer includes that the content of pore creating material is
a2,；
The rest may be inferred, prepares i-th layer of sub-layer, also, with the content meter of i-th layer of sub-layer, i-th layer of sub-layer includes pore-creating
The content of agent is ai；
Until preparing m layers of sub-layer, also, with the content meter of m layers of sub-layer, the m layers of sub-layer includes pore creating material
Content is am, wherein m is the integer more than or equal to 2, preferably 2~10 integer；
It is folded to obtain the composite positive pole of m layers of sub-layer by being sequentially overlapped 1~m layers in the vertical direction of plus plate current-collecting body
Layer；
High temperature and pressure hot-pressing processing is carried out so that respectively there is sub-layer to the above-mentioned composite positive pole lamination with m layers of sub-layer
It can densely be connected, then, carry out vacuum-sintering, form hole after decomposing these pore creating materials, obtain that there is porous gradient
Composite positive pole layer, and pore creating material leaves the hole of same size after high temperature sintering volatilization is decomposed.
Then, the composite positive pole layer with porous gradient is filled using solid electrolyte slurry, to obtain
Anode composite；The mode of filling can be to coat solid electrolyte slurry on positive electrode material layer and keep solid electrolyte slurry complete
Full impregnating porous structure.
According to one embodiment, anode composite layer 102 may include 3 sub-layers, i.e. m=3, sub-layer as shown in Figure 1
1021,1022 and 1023.
Anode composite layer 102 also may include more sub-layers, such as 4,5,6,8,10 layers or more sub-layers.
It should be pointed out that solid electrolyte and solid electrolyte layer in the anode composite layer of the solid electrolyte containing gradient
In solid electrolyte may be the same or different, but convenient for preparation, in general, the solid electrolyte in solid electrolyte layer
As prepare solid electrolyte slurry used in anode composite layer.
Specific preparation process is as follows for anode composite of the invention:
(1) composite positive pole slurry is prepared first, by positive active material, conductive agent, bonding agent, pore creating material, is divided
Powder, plasticizer are mixed and are formed.
The positive active material of the composite positive pole is LiFePO4 (LiFePO4), cobalt acid lithium (LiCoO2), mangaic acid
Lithium (LiMnO2), lithium nickelate (LiNiO2), high manganese lithium (LiMn2O4), one of tertiary cathode material (NCM, NCA) or more
Kind, quality accounts for 60wt%~90wt% of anode composite quality.
The conductive agent of the composite positive pole is conductive carbon black (SP), acetylene black (AB), Ketjen black (KB), vapor phase growth
One of carbon fiber (VGCF), carbon nanotube (CNT), graphene or it is a variety of, quality accounts for the 2wt% of anode composite quality
~10wt%.
The pore creating material of the composite positive pole is poly (methyl methacrylate) micro-sphere (PMMA), starch, carbon dust, bicarbonate
One of ammonium, PS microballoon are a variety of, and quality accounts for 2wt%~10wt% of anode composite.The partial size of the pore creating material is 5~15
μm, and the porosity in the gap finally left in composite positive pole is 5%~20%.
The dispersing agent of the composite positive pole be one of Sodium Polyacrylate, polyacrylic acid ammonia, fish oil or a variety of,
Quality accounts for 2wt%~5wt% of anode composite.
The plasticizer of the composite positive pole is BBP(Butyl Benzyl Phthalate (BBP), in polyethylene glycol (PEG), glycerol
It is one or more, quality accounts for 2wt%~5wt% of anode composite.
The binder of the composite positive pole in SBR, PVDF, PVDF-HFP, PVB, silica gel, SBS, PEG one
Kind is several.It is identical or different with the binder in solid electrolyte slurry.Its quality account for the 2wt% of anode composite quality~
10wt%.
Specifically, by above-mentioned stand-by positive active material powder, conductive agent powder, bonding agent powder, pore creating material powder
It is placed in drying box and is dried 12h, drying temperature is 80 DEG C~120 DEG C；
(2) positive active material, conductive agent, bonding agent, pore creating material, dispersing agent, plasticizer are weighed in proportion and are placed on
In ball mill container, solvent is proportionally then added in ball mill container and (is selected from water (H2O), methanol (CH3OH), ethyl alcohol
(C2H6O), heptane (C7H16), toluene (C7H8), dimethylbenzene (C8H10), butyl butyrate (C8H16O2), N-Methyl pyrrolidone
(C5H9NO), methyl iso-butyl ketone (MIBK) (C6H12O), nitrile (C2N3H), tetrahydrofuran (C4H8O), ether (C4H10One of) O or
It is several), by ball mill container be sealed and vacuumize process and by the revolving speed ball milling of 300r/min~800r/min for 24 hours~36h
It obtains being uniformly mixed anode composite slurry；
(3) the mixed uniformly anode composite slurry that step (2) ball milling is prepared on a pet film, then will be scraped
Being adjusted to 10~80 μm with the spacing of foil and carrying out coating process for knife, the anode composite pole piece that coating is completed is transferred to very
Empty drying box and dry 6~for 24 hours, drying temperature is 100 DEG C~200 DEG C, and vacuum degree is -40~-120Kpa, finally obtains certain
The anode composite pole piece of the pore creating material of one component.
(4) ratio of the pore creating material in anode composite slurry is gradually adjusted in gradient, while according to the step of above-mentioned (2) (3)
Suddenly the sub-layer of the anode composite pole piece of different pore creating material components is prepared.
(5) sub-layer of the anode composite pole piece of different component prepared in (4) is suitable according to the composition gradient of pore creating material
Sequence superposition, hot pressing 2h~5h is in close contact each layer anode composite at being 80 DEG C~200 DEG C in temperature, and the pressure of hot pressing is
30Mpa~70Mpa；Laminated material after hot pressing is subjected to vacuum-sintering at 500 DEG C~700 DEG C, vacuum degree is -20~-
100Kpa obtains the anode composite layer with porous gradient-structure after the completion of sintering.
(6) the solid electrolyte slurry of preparation is coated in the anode composite layer with porous gradient-structure of above-mentioned preparation
And make solid electrolyte slurry complete wetting porous structure, and vacuum oven and dry 12~for 24 hours is transferred it to, it is dry
Temperature is 80 DEG C~200 DEG C, and vacuum degree is -40~-120Kpa, finally obtains the anode pole piece of the solid electrolyte containing gradient.
It should be pointed out that the mode of the adjustment pore creating material gradient in step (4) can successively decrease for equal difference, or uniformly successively decrease,
Or other decreasing fashions, as long as the gradient for meeting pore creating material is to successively decrease from the gradient of positive foil 101 from high to low
?.In addition, the gross mass that the content of the pore creating material in all anode sub-layers accounts for anode composite is 2wt~10wt%, Ke Yili
It solving, the content of the pore creating material in any anode sub-layer can be greater than the 10wt% of the sub-layer quality, but not more than 20wt%,
But it is not less than 1%.
For example, it is any anode sub-layer in pore creating material content can for 20wt%, 19wt%, 18wt%, 17wt%,
16wt%, 15wt% etc., or 1wt%, 2wt%, 3wt%, 4wt%, 5wt% etc..
According to one embodiment, in the vertical direction away from plus plate current-collecting body, relative to the quality of each positive sub-layer,
The content of pore creating material is followed successively by 15wt%, 12wt%, 9wt%, 6wt%, 3wt% in 1st~5 sub-layer.
Correspondingly, in the vertical direction away from plus plate current-collecting body, the porosity ranges of each sub-layer are to be passed by 3%~10%
Reduce to 1%~4%, for example, in one embodiment, the porosity in the 1st~5 sub-layer is followed successively by 9%, 7.2%, 5.4%,
3.6%, 1.8%.
Obtain having the hole in the anode composite layer of porous gradient-structure by solid electrolytic after the completion of sintering in step (5)
Therefore matter filled therewith both contains composite positive pole in anode composite layer, also containing the solid electrolyte of gradient.
3, the cathode pole piece of the solid electrolyte containing gradient is prepared
There is the composite negative pole layer 202 of porous gradient firstly the need of preparation, for this purpose, what the present invention used answers
It closes negative electrode layer 202 and needs to be divided into multiple sub-layers, the pore creating material of different content is wherein used in these sub-layers, is made in each sub-layer
Content of Pore-forming Agents is more, and the quantity of the micropore subsequently formed is also more.Therefore Graded amounts are used in these sub-layers
Pore creating material, the negative electrode material layer being made of these sub-layers just has the pore creating material of Graded amounts, after shaping, these pore creating materials
Hole is formed after decomposition, obtains the composite negative pole layer 202 with porous gradient, and pore creating material stays after high temperature sintering volatilization is decomposed
The hole of lower same size.
That is: the 1st layer of composite negative pole material layer sub-layer is prepared, wherein first with the content meter of the 1st layer of sub-layer, the 1st layer of sub-layer
Content comprising pore creating material is a1,；
Prepare the 2nd layer of sub-layer, wherein with the content meter of the 1st layer of sub-layer, the 2nd layer of sub-layer includes that the content of pore creating material is
a2,；
The rest may be inferred, prepares jth layer sub-layer, also, with the content meter of jth layer sub-layer, i-th layer of sub-layer includes pore-creating
The content of agent is aj；
Until preparing n-th layer sub-layer, also, with the content meter of n-th layer sub-layer, the n-th layer sub-layer includes pore creating material
Content is an, wherein n is the integer more than or equal to 2, preferably 2~10 integer；
It is folded to obtain the composite negative pole material of n-layer sub-layer by 1~n-layer is sequentially overlapped in the vertical direction of negative current collector
Layer；
High temperature and pressure hot-pressing processing is carried out so that respectively there is sub-layer to the above-mentioned composite negative pole material lamination with n-layer sub-layer
It can densely be connected, then, carry out vacuum-sintering, form hole after decomposing these pore creating materials, obtain that there is porous gradient
Composite negative pole material layer, and pore creating material leaves the hole of same size after high temperature sintering volatilization is decomposed.
Then, the composite negative pole material layer with porous gradient is filled using solid electrolyte slurry, to obtain
Composite negative pole；The mode of filling can be to coat solid electrolyte slurry on negative electrode material layer and keep solid electrolyte slurry complete
Full impregnating porous structure.
According to one embodiment, composite negative pole layer 202 may include 3 sub-layers, i.e. n is 3, sub-layer as shown in Figure 1
2021,2022 and 2023.
Similar with anode, the mode of filling can coat solid electrolyte slurry on composite negative pole layer and make solid electrolytic
Chylema material complete wetting is in porous structure.
It should be pointed out that solid electrolyte and solid electrolyte layer in the composite negative pole layer of the solid electrolyte containing gradient
In solid electrolyte may be the same or different, but convenient for preparation, in general, the solid electrolyte in solid electrolyte layer
As prepare solid electrolyte slurry used in composite negative pole material layer.
Composite negative pole of the invention specific the preparation method is as follows:
(1) composite negative pole material slurry is prepared first, by negative electrode active material, conductive agent, bonding agent, pore creating material, is divided
Powder and plasticizer composition.
The negative electrode active material of the composite negative pole material is graphite, lithium titanate, elemental silicon, silicon-carbon cathode, lithium metal, lithium
One of alloy is a variety of, and quality accounts for 60wt%~90wt% of composite negative pole quality.
Similar with the conductive agent of the composite positive pole, the conductive agent of the composite negative pole material is conductive carbon black
(SP), one of acetylene black (AB), Ketjen black (KB), gas-phase growth of carbon fibre (VGCF), carbon nanotube (CNT), graphene
Or it is a variety of, quality accounts for 2wt%~10wt% of composite negative pole quality.
The conductive agent of the composite positive pole and the conductive agent of the composite negative pole material are identical or different, for example, lead
Electrical carbon black (SP), acetylene black (AB), Ketjen black (KB), gas-phase growth of carbon fibre (VGCF), carbon nanotube (CNT), in graphene
One kind or it is a variety of, quality accounts for 2wt%~10wt% of composite negative pole quality.
The pore creating material of the composite negative pole material and the pore creating material of the composite positive pole are identical or different, for example, poly-
One of methyl methacrylate microballoon (PMMA), starch, carbon dust, ammonium hydrogen carbonate, PS microballoon are a variety of, quality accounts for multiple
2wt%~10wt% of cathode and composite negative pole gross mass is closed, the partial size of the pore creating material is 5~15 μm, and the sky finally left
The porosity of gap is 5%~20%.
The dispersing agent of the composite negative pole material and the dispersing agent of the composite positive pole are identical or different, for example, poly-
One of sodium acrylate, polyacrylic acid ammonia, fish oil are a variety of, and quality accounts for 2wt%~5wt% of composite negative pole gross mass.
The dispersing agent of the composite positive pole and the dispersing agent of the composite negative pole material are identical or different, for example, poly-
One of methyl methacrylate microballoon (PMMA), starch, carbon dust, ammonium hydrogen carbonate, PS microballoon are a variety of, and quality accounts for compound
2wt%~10wt% of cathode gross mass.
The plasticizer of the composite negative pole material and the plasticizer for stating composite negative pole material are identical or different, for example,
One of BBP(Butyl Benzyl Phthalate (BBP), polyethylene glycol (PEG), glycerol are a variety of, and quality accounts for composite negative pole gross mass
2wt%~5wt%.
The binder of the composite negative pole material and the binder for stating composite negative pole material are identical or different, for example,
One or more of SBR, PVDF, PVDF-HFP, PVB, silica gel, SBS, PEG.Itself and the binder in solid electrolyte slurry
It is identical or different.Its quality accounts for 2wt%~10wt% of composite negative pole quality.
It is similar with the preparation method of anode composite pole piece, specifically, by above-mentioned stand-by positive active material powder, conduction
Agent powder, bonding agent powder, pore creating material powder, which are placed in drying box, is dried 12h, and drying temperature is 80 DEG C~120 DEG C；
(2) negative electrode active material, conductive agent, bonding agent, pore creating material, dispersing agent, plasticizer are weighed in proportion and are placed on
In ball mill container, solvent is proportionally then added in ball mill container and (is selected from water (H2O), methanol (CH3OH), ethyl alcohol
(C2H6O), heptane (C7H16), toluene (C7H8), dimethylbenzene (C8H10), butyl butyrate (C8H16O2), N-Methyl pyrrolidone
(C5H9NO), methyl iso-butyl ketone (MIBK) (C6H12O), nitrile (C2N3H), tetrahydrofuran (C4H8O), ether (C4H10One of) O or
It is several), by ball mill container be sealed and vacuumize process and by the revolving speed ball milling of 300r/min~800r/min for 24 hours~36h
It obtains being uniformly mixed composite negative pole slurry；
(3) the mixed uniformly composite negative pole slurry that step (2) ball milling is prepared on a pet film, then will be scraped
Being adjusted to 10~80 μm with the spacing of foil and carrying out coating process for knife, the composite negative pole pole piece that coating is completed is transferred to very
Empty drying box and dry 6~for 24 hours, drying temperature is 100 DEG C~200 DEG C, and vacuum degree is -40~-120Kpa, finally obtains certain
The composite negative pole pole piece of the pore creating material of one component.
(4) ratio of the pore creating material in composite negative pole slurry is gradually adjusted in gradient, while according to the step of above-mentioned (2) (3)
Suddenly the composite negative pole pole piece of different component is prepared.
(5) by the composite negative pole pole piece of different component prepared in (4) according to the composition gradient laminated structure of pore creating material,
Hot pressing 2h~5h is in close contact each layer composite negative pole at being 80 DEG C~200 DEG C in temperature, the pressure of hot pressing be 30Mpa~
70Mpa；Laminated material after hot pressing is subjected to vacuum-sintering at 500 DEG C~700 DEG C, vacuum degree is -20~-100Kpa,
The composite negative pole layer with porous gradient-structure is obtained after the completion of sintering.
(6) the solid electrolyte slurry of preparation is coated in the composite negative pole layer with porous gradient-structure of above-mentioned preparation
And make solid electrolyte slurry complete wetting in porous structure, vacuum oven and dry 12~for 24 hours is transferred it to,
Drying temperature is 80 DEG C~200 DEG C, and vacuum degree is -40~-120Kpa, finally obtains the cathode pole of the solid electrolyte containing gradient
Piece 202.
It should be appreciated that the case where with described in anode is similar, the mode of the adjustment pore creating material gradient in step (4) can be
Equal difference is successively decreased, or is uniformly successively decreased, or other decreasing fashions, as long as the gradient for meeting pore creating material is from cathode
The gradient of foil 201 from high to low is successively decreased.In addition, the content of the pore creating material in all cathode sub-layers accounts for the total of composite negative pole
Quality is 2wt~10wt%, it will be understood that the content of the pore creating material in any cathode sub-layer can be greater than the sub-layer quality
10wt%, but not more than 20wt%, but it is not less than 1%.
For example, the content of the pore creating material in any cathode sub-layer can for 20wt%, 19wt%, 18wt%, 17wt%,
16wt%, 15wt% etc., or 1wt%, 2wt%, 3wt%, 4wt%, 5wt% etc..
According to one embodiment, the quality relative to each cathode sub-layer, the content of pore creating material in the 1st~5 cathode sub-layer
It is followed successively by 15wt%, 12wt%, 9wt%, 6wt%, 3wt%.
Correspondingly, in the vertical direction away from negative current collector, the porosity ranges of each sub-layer are to be passed by 3%~10%
Reduce to 1%~4%, for example, in one embodiment, the porosity in the 1st~5 sub-layer is followed successively by 9%, 7.2%, 5.4%,
3.6%, 1.8%.
Obtain having the hole in the composite negative pole layer of porous gradient-structure by solid electrolytic after the completion of sintering in step (5)
Therefore matter filled therewith both contains composite negative pole material in composite negative pole layer, also containing the solid electrolyte of gradient.
Row hot pressing and pressure maintaining processing are added into anode composite layer obtained above, solid electrolyte layer, composite negative pole stacking,
Wherein pressure is 20Mpa~80Mpa, and temperature is 30 DEG C~80 DEG C, and the dwell time is 30s~180s, finally obtains all solid lithium
Ion battery.
Embodiment 1
(1) preparation of solid electrolyte pole piece
By stand-by Li7La3Zr2O12(LLZO) it is 100 that solid electrolyte powder, binder (SBR) powder, which are placed in temperature,
It is dried 10h in drying box at DEG C, then accounts for 90wt% in solid electrolyte powder, binder accounts for the ratio of 10wt% and claims
It takes and is placed in ball mill container, nmp solvent then is added according to the 15wt% of powder gross mass, ball mill container is sealed
It obtains being uniformly mixed solid electrolyte slurry by the revolving speed ball milling 5h of 400r/min at 45 DEG C after processing；Consolidate what is be uniformly mixed
Body electrolyte slurry is poured on aluminium foil, and being adjusted to 30 μm with the spacing of foil and carrying out coating process for scraper is then transferred into
Drying temperature is 80 DEG C, and vacuum degree is -80Kpa vacuum oven and dry 10h, finally obtains the solid electricity with a thickness of 20 μm
Solve matter pole piece.
(2) preparation of the anode composite pole piece of porous gradient-structure
By stand-by LiFePO4 (LiFePO4) positive active material powder, acetylene black (AB) conductive agent powder, binder
(SBR) it is the interior drying process 6h of drying box at 100 DEG C that powder, pore creating material (PMMA microsphere) powder, which are placed in temperature, is then pressed
It is gradually decreased by 15wt%~3wt% by positive active material, conductive agent, bonding agent, pore creating material, dispersion according to the ratio of pore creating material
Agent, plasticizer (relative to the quality of each sub-layer, the ratio in five sub-layers be respectively 1. 75wt%, 5wt%, 2wt%, 15wt%,
2wt%, 1wt%；2. 78wt%, 5wt%, 2wt%, 12wt%, 2wt%, 1wt%；3. 81wt%, 5wt%, 2wt%,
9wt%, 2wt%, 1wt%；4. 84wt%, 5wt%, 2wt%, 6wt%, 2wt%, 1wt%；5. 87wt%, 5wt%,
2wt%, 3wt%, 2wt%, 1wt%；) nmp solvent is weighed and is placed in ball grinder and is added, ball mill container is sealed
It obtains being uniformly mixed containing the compound of above-mentioned different pore creating material components by the revolving speed ball milling 3h of 350r/min at 60 DEG C after processing
Anode sizing agent；Respectively on a pet film by uniformly mixed anode composite slurry, scraper with the spacing of foil is adjusted to 25 μm simultaneously
It is coated technique, being then transferred into drying temperature is 60 DEG C, and vacuum degree is -60Kpa vacuum oven and dries 8h, finally
Obtain the anode composite pole piece of different pore creating material components, the anode composite pole piece of the different component of preparation according to pore creating material component
Gradient sequence's superposition, hot pressing 2h is in close contact each layer anode composite at being 120 DEG C in temperature, and the pressure of hot pressing is 50Mpa；It will
Laminated material after hot pressing carries out vacuum-sintering at 500 DEG C, and vacuum degree is -20~-100Kpa, is had after the completion of sintering
There is the anode composite layer of porous gradient-structure.
Then, the solid electrolyte slurry of preparation is coated in the anode composite with porous gradient-structure of above-mentioned preparation
Layer simultaneously makes solid electrolyte slurry complete wetting in porous structure, transfer it to vacuum oven and dry 12~
For 24 hours, drying temperature is 80 DEG C~200 DEG C, and vacuum degree is -40~-120Kpa, finally obtains anode composite and solid electrolyte
Lamination.
(3) preparation of the composite negative pole pole piece of porous gradient-structure
By stand-by silicon-carbon (Si/C) negative electrode active material powder, acetylene black (AB) conductive agent powder, binder (SBR) powder
It is the interior drying process 6h of drying box at 100 DEG C that body, pore creating material (PMMA microsphere) powder, which are placed in temperature, then according to pore creating material
Ratio gradually decreased by 15wt%~3wt% by negative electrode active material, conductive agent, bonding agent, pore creating material, dispersing agent, plasticising
(weight ratio in five sub-layers is respectively as follows: 1. 75wt%, 5wt%, 2wt%, 15wt%, 2wt%, 1wt% for agent；②
78wt%, 5wt%, 2wt%, 12wt%, 2wt%, 1wt%；3. 81wt%, 5wt%, 2wt%, 9wt%, 2wt%, 1wt%；
4. 84wt%, 5wt%, 2wt%, 6wt%, 2wt%, 1wt%；5. 87wt%, 5wt%, 2wt%, 3wt%, 2wt%,
1wt%；) weigh and be placed in ball grinder and be added nmp solvent, by ball mill container be sealed processing after at 60 DEG C by
The revolving speed ball milling 3h of 350r/min obtains being uniformly mixed the composite negative pole slurry containing different pore creating material components；It will mix respectively equal
Even composite negative pole slurry on a pet film, then shift by being adjusted to 25 μm with the spacing of foil and carrying out coating process for scraper
It is 60 DEG C to drying temperature, vacuum degree is -60Kpa vacuum oven and dry 8h, finally obtains answering for different pore creating material components
Cathode pole piece is closed, the composite negative pole pole piece of 5 components of preparation is in temperature according to the composition gradient laminated structure of pore creating material
Hot pressing 2h is in close contact each layer composite negative pole at 120 DEG C, and the pressure of hot pressing is 50Mpa；By the laminated material after hot pressing 500
Vacuum-sintering is carried out at DEG C, vacuum degree is -20~-100Kpa, obtains having the compound of porous gradient-structure after the completion of sintering
Negative electrode layer.The solid electrolyte slurry of preparation is coated in the composite negative pole layer with porous gradient-structure of above-mentioned preparation and is made
Solid electrolyte slurry complete wetting transfers it to vacuum oven and drying for 24 hours, drying temperature in porous structure
It is 80 DEG C, vacuum degree is -40~-120Kpa, finally obtains composite negative pole and solid electrolyte lamination.
(4) preparation of all solid lithium secondary battery
By the anode composite of above-mentioned preparation and solid electrolyte lamination, solid electrolyte pole piece, composite negative pole and solid electricity
It solves the superposition of matter lamination trilaminate material and carries out hot pressing and pressure maintaining processing, wherein pressure is 20Mpa, and temperature is 50 DEG C, and the dwell time is
30s finally obtains all-solid lithium-ion battery
Embodiment 2:
(1) preparation of solid electrolyte pole piece
By stand-by Li10GeP2S12(LGPS) it is 100 that solid electrolyte powder, binder (SBS) powder, which are placed in temperature,
It is dried 10h in drying box at DEG C, then accounts for 85wt% in solid electrolyte powder, binder accounts for the ratio of 15wt% and claims
It takes and is placed in ball mill container, dimethylbenzene (C then is added according to the 15wt% of powder gross mass8H10) solvent, ball milling is held
Device, which is sealed, to be obtained being uniformly mixed solid electrolyte slurry by the revolving speed ball milling 5h of 450r/min at 45 DEG C after processing；It will mix
Uniform solid electrolyte slurry is closed to be poured on aluminium foil, scraper is adjusted to 40 μm with the spacing of foil and carries out coating process,
Being then transferred into drying temperature is 80 DEG C, and vacuum degree is -80Kpa vacuum oven and dry 10h, finally obtains solid electrolytic
Matter pole piece.
(2) preparation of the anode composite pole piece of porous gradient-structure
By stand-by cobalt acid lithium (LiCoO2) positive active material powder, carbon nanotube (CNT) conductive agent powder, binder
(SBS) powder, pore creating material (PS microballoon) powder be placed in temperature be 100 DEG C at drying box in be dried 6h, then according to
The ratio of pore creating material is gradually decreased by 15wt%~3wt% by positive active material, conductive agent, bonding agent, pore creating material, dispersion
(weight ratio in five sub-layers is respectively as follows: 1. 75wt%, 5wt%, 2wt%, 15wt%, 2wt%, 1wt% for agent, plasticizer；
2. 78wt%, 5wt%, 2wt%, 12wt%, 2wt%, 1wt.%；3. 81wt%, 5wt%, 2wt%, 9wt%, 2wt%,
1wt%；4. 84wt%, 5wt%, 2wt%, 6wt%, 2wt%, 1wt%；5. 87wt%, 5wt%, 2wt%, 3wt%,
2wt%, 1wt%；) weigh and be placed in ball grinder and dimethylbenzene (C is added8H10) solvent, ball mill container is sealed place
Obtain being uniformly mixed the anode composite slurry containing different pore creating material components after reason by the revolving speed ball milling 5h of 400r/min at 60 DEG C
Material；Respectively on a pet film by uniformly mixed anode composite slurry, scraper is adjusted to 35 μm with the spacing of foil and is applied
Cloth technique, being then transferred into drying temperature is 80 DEG C, and vacuum degree is -80Kpa vacuum oven and dry 8h, is finally obtained not
With the anode composite pole piece of pore creating material component, the anode composite pole piece of the different component of preparation is suitable according to the composition gradient of pore creating material
Sequence superposition, hot pressing 5h is in close contact each layer anode composite at being 100 DEG C in temperature, and the pressure of hot pressing is 60Mpa；After hot pressing
Laminated material carry out vacuum-sintering at 800 DEG C, vacuum degree is -20~-100Kpa, obtains having after the completion of sintering porous
The anode composite layer of gradient-structure.By the solid electrolyte slurry of preparation be coated in above-mentioned preparation with porous gradient-structure
Anode composite layer simultaneously makes solid electrolyte slurry complete wetting in porous structure, transfers it to vacuum oven and does
Dry 12h, drying temperature are 100 DEG C, and vacuum degree is -40~-120Kpa, finally obtain anode composite and solid electrolyte is folded
Layer.
(3) preparation of the composite negative pole pole piece of porous gradient-structure
By stand-by graphite cathode active material powder, carbon nanotube (CNT) conductive agent powder, binder (SBS) powder,
It is the interior drying process 6h of drying box at 100 DEG C that pore creating material (PS microballoon) powder, which is placed in temperature, then according to the ratio of pore creating material
Example is gradually decreased by 15wt%~3wt%.By negative electrode active material, conductive agent, bonding agent, pore creating material, dispersing agent, plasticizer
(weight ratio in five sub-layers is respectively as follows: 1. 75wt%, 5wt%, 2wt%, 15wt%, 2wt%, 1wt%；2. 78wt%,
5wt%, 2wt%, 12wt%, 2wt%, 1wt%；3. 81wt%, 5wt%, 2wt%, 9wt%, 2wt%, 1wt%；④
84wt%, 5wt%, 2wt.%, 6wt%, 2wt%, 1wt%；5. 87wt%, 5wt%, 2wt%, 3wt%, 2wt%,
1wt%；) weigh and be placed in ball grinder and dimethylbenzene (C is added8H10) solvent, ball mill container is sealed after handling
It obtains being uniformly mixed the composite negative pole slurry containing different pore creating material components by the revolving speed ball milling 5h of 400r/min at 60 DEG C；Respectively
On a pet film by uniformly mixed composite negative pole slurry, scraper is adjusted to 35 μm with the spacing of foil and carries out coating process,
Being then transferred into drying temperature is 80 DEG C, and vacuum degree is -80Kpa vacuum oven and dry 8h, finally obtains different pore creating materials
The composite negative pole pole piece of component, the composite negative pole pole piece of the different component of preparation according to pore creating material composition gradient laminated structure,
Hot pressing 5h is in close contact each layer composite negative pole at being 100 DEG C in temperature, and the pressure of hot pressing is 60Mpa；By the lamination after hot pressing
Material carries out vacuum-sintering at 800 DEG C, and vacuum degree is -20~-100Kpa, obtains having porous gradient knot after the completion of sintering
The composite negative pole layer of structure.The solid electrolyte slurry of preparation is coated in the Compound Negative with porous gradient-structure of above-mentioned preparation
Pole layer simultaneously makes solid electrolyte slurry complete wetting in porous structure, transfers it to vacuum oven and dry 12h,
Drying temperature is 100 DEG C, and vacuum degree is -40~-120Kpa, finally obtains composite negative pole and solid electrolyte lamination.
(4) preparation of all solid lithium secondary battery
By the anode composite of above-mentioned preparation and solid electrolyte lamination, solid electrolyte pole piece, composite negative pole and solid electricity
It solves the superposition of matter lamination trilaminate material and carries out hot pressing and pressure maintaining processing, wherein pressure is 80Mpa, and temperature is 80 DEG C, and the dwell time is
100s finally obtains all-solid lithium-ion battery.
Comparative example 1
(1) preparation of solid electrolyte pole piece
By stand-by Li7La3Zr2O12(LLZO) it is 100 that solid electrolyte powder, binder (SBS) powder, which are placed in temperature,
It is dried 10h in drying box at DEG C, then accounts for 85wt% in solid electrolyte powder, binder accounts for the ratio of 15wt% and claims
It takes and is placed in ball mill container, heptane (C then is added according to the 15wt% of powder gross mass7H16) solvent, by ball mill container
It is sealed and obtains being uniformly mixed solid electrolyte slurry by the revolving speed ball milling 5h of 550r/min at 45 DEG C after processing；It will mixing
Uniform solid electrolyte slurry is poured on aluminium foil, and scraper is adjusted to 40 μm with the spacing of foil and carries out coating process, so
After to be transferred to drying temperature be 80 DEG C, vacuum degree is -80Kpa vacuum oven and dry 10h, finally obtains solid electrolyte
Pole piece.
(2) preparation of anode composite pole piece
By stand-by tertiary cathode (NCM) active material powder, carbon nanotube (CNT) conductive agent powder, binder (SBS)
Powder, solid electrolyte powder Li7La3Zr2O12(LLZO) being placed in temperature is the interior drying process 6h of drying box at 100 DEG C, so
Afterwards by positive active material, conductive agent, bonding agent, solid electrolyte (ratio be respectively 90wt%, 5wt%, 2wt%,
3wt%；) weigh and be placed in ball mill container and heptane (C is added7H16) solvent, ball mill container is sealed after handling
It obtains being uniformly mixed by the revolving speed ball milling 5h of 400r/min at 60 DEG C and obtains anode composite slurry；Uniformly mixed anode composite is starched
On a pet film, scraper is adjusted to 35 μm with the spacing of foil and carries out coating process material, and being then transferred into drying temperature is
80 DEG C, vacuum degree is -80Kpa vacuum oven and dry 8h, finally obtains anode composite pole piece, compound by what is be prepared
Hot pressing 5h is in close contact anode composite at anode pole piece is 100 DEG C in temperature, and the pressure of hot pressing is 60Mpa；Then by its turn
Move on to vacuum oven and dry 12h, drying temperature is 100 DEG C, and vacuum degree is -40~-120Kpa, finally obtain it is compound just
Pole pole piece.
(3) preparation of composite negative pole pole piece
By stand-by graphite cathode active material powder, carbon nanotube (CNT) conductive agent powder, binder (SBS) powder,
Solid electrolyte powder Li7La3Zr2O12(LLZO) being placed in temperature is the interior drying process 6h of drying box at 100 DEG C, then will
(ratio is respectively 90wt%, 5wt%, 2wt%, 3wt% for negative electrode active material, conductive agent, bonding agent, solid electrolyte；) claim
It takes and is placed in ball mill container and heptane (C is added7H16) solvent, by ball mill container be sealed processing after at 60 DEG C by
The revolving speed ball milling 5h of 400r/min obtains uniformly mixed composite negative pole slurry；Uniformly mixed composite negative pole slurry is poured on PET
On film, scraper is adjusted to 35 μm with the spacing of foil and carries out coating process, and being then transferred into drying temperature is 80 DEG C, vacuum
Degree is -80Kpa vacuum oven and dry 8h, finally obtains composite negative pole pole piece, the composite negative pole pole piece being prepared is existed
Temperature is that hot pressing 5h is in close contact composite negative pole at 100 DEG C, and the pressure of hot pressing is 60Mpa；It is dry to transfer it to vacuum
Dry case and dry 12h, drying temperature are 100 DEG C, and vacuum degree is -40~-120Kpa, finally obtains composite negative pole pole piece.
(4) preparation of all solid lithium secondary battery
The anode composite layer of above-mentioned preparation, solid electrolyte pole piece, the superposition of composite negative pole layer trilaminate material are subjected to hot pressing
And pressure maintaining is handled, wherein pressure is 80Mpa, and temperature is 80 DEG C, dwell time 100s, finally obtains all solid state lithium ion electricity
Pond.
Test case:
Interface impedance and cycle performance test are measured to all-solid-state battery prepared by above embodiments 1 and comparative example 1.Entirely
The measuring method of solid state battery interface impedance are as follows: carry out the all-solid-state battery of above-mentioned preparation in electrochemical test system respectively
Static test, test frequency range are 10Hz~10MHz, and the positive and negative disturbance sinusoidal voltage of application is 5mV.All-solid-state battery circulation
Property test method are as follows: the all-solid-state battery of above-mentioned preparation is tested in the enterprising Mobile state of blue electrical measurement test system respectively, test
Multiplying power is 1C, and the temperature of test is 25 DEG C.Interface impedance value such as Fig. 3 institute of all-solid-state battery in testing example 1 and comparative example
Show.As seen from Figure 3, the impedance value of the battery of the method for the present invention preparation significantly improves, the all-solid-state battery in comparative example
Interface impedance is 111.3 Ω, and the interface impedance of battery prepared by the present invention is used to be reduced to 70.2 Ω.Testing example 1 with
The cycle performance of all-solid-state battery is as shown in Figure 4 in comparative example.From fig. 4, it can be seen that all-solid-state battery prepared by the present invention is in 100 circles
Capacity retention ratio after 1C circulation is 91.3%, and capacity of the all-solid-state battery in comparative example after 100 circle 1C circulations is kept
Rate is 85.4%.
The all-solid-state battery prepared using comparative example 1 and Examples 1 to 2 method is subjected to interface impedance survey at room temperature
Examination, cycle performance test, acquired results are shown in Table 1.
The interface impedance of all-solid-state battery, cycle performance test result in 1 comparative example 1 of table and Examples 1 to 2
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (12)
1. a kind of all-solid lithium-ion battery, comprising:
Anode pole piece with composite positive pole layer, the cathode pole piece with composite negative pole material layer and it is located at the positive pole
Solid electrolyte between piece and the cathode pole piece, it is characterised in that:
The composite positive pole layer has micropore, and the porosity of micropore is passed in the vertical direction away from plus plate current-collecting body
Subtract；With
The composite negative pole material layer has micropore, and the porosity of micropore is passed in the vertical direction away from negative current collector
Subtract,
Wherein, the micropore is at least partly filled by solid electrolyte.
2. all-solid lithium-ion battery according to claim 1, wherein the overall porosity of the micropore is 5%~20%,
The aperture of the micropore is 5~15 μm.
3. all-solid lithium-ion battery according to claim 1 or 2, wherein the solid electrolyte it is described it is compound just
It is in net distribution in pole material layer and the composite negative pole material layer.
4. all-solid lithium-ion battery described in any one of claim 1 to 3, wherein the micropore is by content in ladder
The pore creating material of degree distribution is formed, and based on the gross mass of the composite positive pole layer, the pore creating material is in the anode composite material
Total amount in the bed of material is 2~10wt%, and the gross mass based on the composite negative pole material layer, and the pore creating material is described compound
Total amount in negative electrode material layer is 2~10wt%.
5. all-solid lithium-ion battery according to claim 4, wherein the pore creating material is selected from polymethyl methacrylate
One of microballoon (PMMA), starch, carbon dust, ammonium hydrogen carbonate, PS microballoon are a variety of.
6. solid lithium ion battery according to claim 4, wherein the partial size of the pore creating material is 5~15 μm.
7. all-solid lithium-ion battery according to any one of the preceding claims, wherein the composite positive pole layer
It being made of m layers of sub-layer, wherein the porosity of micropore is gradually successively decreased by the 1st layer adjacent with plus plate current-collecting body in i-th layer of sub-layer,
The wherein integer that m is 2~10, i are the integer of 1~m；And the composite negative pole material layer is made of n-layer sub-layer, wherein jth is sub-
The porosity of micropore is gradually successively decreased by the 1st layer adjacent with negative current collector in layer, wherein the integer that n is 2~10, j are 1~n
Integer.
8. all-solid lithium-ion battery according to claim 7, wherein the sub-layer with a thickness of 10~80 μm.
9. the method for preparing all-solid lithium-ion battery described in any one of preceding claims, which comprises
The pore creating material of different content is mixed to get anode composite sub-layer with composite positive pole respectively, and by the pore creating material
The sequence that content is successively decreased in the vertical direction away from plus plate current-collecting body is successively laminated the anode composite sub-layer, then
Pore creating material is set to form the micropore；
The pore creating material of different content is mixed to get composite negative pole sub-layer with composite negative pole material respectively, and by the pore creating material
The sequence that content is successively decreased in the vertical direction away from plus plate current-collecting body is successively laminated the composite negative pole sub-layer, then
Pore creating material is set to form the micropore；
Wherein, the micropore is filled using solid electrolyte.
10. according to the method described in claim 9, wherein, the pore creating material of m group different content is mixed with composite positive pole respectively
Conjunction forms m layers of anode composite sub-layer, wherein the integer that m is 2~10, and
The pore creating material of n group different content is mixed to form n-layer anode composite sub-layer with composite positive pole respectively, wherein n 2
~10 integer.
11. according to the method described in claim 9, wherein, the pore creating material 500 DEG C~850 DEG C temperature, -20~-
Vacuum-sintering is carried out under the vacuum degree of 100Kpa to form the micropore.
12. according to the method described in claim 9, being that will be formed with the mode that solid electrolyte fills the micropore wherein
The lamination of micropore is immersed in the slurry of solid electrolyte.
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| CN111312985A (en) * | 2020-02-27 | 2020-06-19 | 湖北亿纬动力有限公司 | Pole piece with porosity gradient distribution as well as preparation method and application thereof |
| CN111725479A (en) * | 2020-07-16 | 2020-09-29 | 深圳市信宇人科技股份有限公司 | Lithium ion battery pole piece and preparation method thereof |
| CN111969252A (en) * | 2020-08-31 | 2020-11-20 | 蜂巢能源科技有限公司 | Solid-state battery and method for manufacturing same |
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| CN114267890A (en) * | 2021-12-28 | 2022-04-01 | 广东国光电子有限公司 | Positive pole piece and preparation method and application thereof |
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| CN114530574A (en) * | 2022-01-25 | 2022-05-24 | 复旦大学 | Structured all-solid-state battery composite positive electrode, preparation method thereof and all-solid-state battery |
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| CN115084440A (en) * | 2022-06-30 | 2022-09-20 | 蜂巢能源科技股份有限公司 | Low-impedance positive pole piece and preparation method and application thereof |
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| CN115295764A (en) * | 2022-07-29 | 2022-11-04 | 江苏正力新能电池技术有限公司 | Negative pole piece, preparation method thereof and secondary battery |
| CN115863643A (en) * | 2022-12-10 | 2023-03-28 | 安徽皓飞新材料有限公司 | Dispersing and softening agent for lithium ion battery anode slurry and application thereof |
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