CN109509910A - A kind of hybrid solid-state electrolyte and preparation method thereof - Google Patents
A kind of hybrid solid-state electrolyte and preparation method thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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Abstract
The invention discloses a kind of hybrid solid-state electrolyte and preparation method thereof, the hybrid solid-state electrolyte includes at least sulfide solid-state electrolyte layer and non-crystal oxide solid-state electrolyte layer.The present invention is by improving the interface problem between sulfide solid electrolyte and electrode material in sulfide solid electrolyte surface recombination non-crystal oxide solid electrolyte；Meanwhile the present invention ensures that heterogeneous interface (oxide/sulfide interface) is compound good by thermoforming way.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of hybrid solid-state electrolyte and its preparation side
Method.
Background technique
Growing digital electric consumption and emerging electric car industry propose higher want to energy storage device
It asks.Lithium secondary battery has that energy density is high, cyclicity is superior, memory-less effect and many advantages, such as non-environmental-pollution, and by
To the favor in market.But using the lithium ion battery of organic electrolyte the higher and higher safety in market, energy density with
And it gradually has too many difficulties to cope in face of the requirement of cycle life etc..
The safety for having liquid lithium secondary battery incomparable using all solid lithium secondary battery of solid electrolyte, and
It is expected to thoroughly eliminate the security risk in use process, more meets the demand of electric car and scale energy storage field future development.
The solid electrolyte studied extensively at present is broadly divided into two classes: polymer dielectric and inorganic electrolyte.Inorganic electrolyte can
It is divided into two class of oxide and sulfide, and oxide and sulfide can be further separated into as crystalline state, devitrified glass state and amorphous state.
Polymer dielectric has the advantages that flexibility, preparation is simple, and density is small, good film-forming property.But polymer dielectric
Room temperature ionic conductivity it is low, be not able to satisfy requirement.Moreover, its bad mechanical property, can not inhibit Li dendrite.
Inorganic electrolyte has many advantages, such as that nonflammable, electrochemical stability window is wide, modulus of shearing is big, has organic electrolyte
The advantages such as incomparable safety and service life.Meanwhile metal can also be used using the solid state battery of solid electrolyte
Lithium abandons diaphragm and negative current collector structure as cathode, to greatly promote energy density.
Oxide electrolyte has very high modulus of shearing, theoretically can effectively inhibit Li dendrite.But oxide is electric
It is relatively low (most to be in 10 to solve matter conductivity at room temperature-6S/cm~10-4It S/cm), still cannot be with organic electrolysis
Liquid phase ratio.And since the oxide electrolyte hardness of crystalline state is larger, when matching with electrode, solid-solid contact is poor, causes big
Interface impedance.Meanwhile hard and crisp oxide electrolyte is easy embrittlement when coping with the volume expansion problem of electrode, thus anxious
Speed deteriorates performance.
Sulfide electrolyte flexible relative, moreover, being obtained with very high ionic conductivity by the method being cold-pressed.
The Li of Thio-LiSICON structure10GeP2S12Conductivity at room temperature reached 1.2 × 10-2S/cm has reached organic electrolysis
The conductivity level of liquid.So high ionic conductivity can effectively improve the energy storage density and power density of all-solid-state battery.
But single sulfide electrolyte still has following problems: (1) the high price Ge in sulfide4+It is unstable to lithium metal, such as
Fruit directly contacts, and can be restored by Li, generates low conductivity miscellaneous phase；(2) sulfide differs greatly with oxide anode chemical potential, and
And electron-ion mixed conductor when oxide electrode, wide Schottky type space charge layer is easily formed, big interface is caused to hinder
It is anti-；(3) the sulfide modulus of shearing of cold moudling is lower, inhibits the effect of Li dendrite undesirable.
As it can be seen that single electrolyte is constantly present short slab in a certain respect in comprehensive performance, it is unable to satisfy solid state battery pair
The requirement of electrolyte comprehensive performance.Therefore, the advantages of how combining the electrolyte of different component, plays the advantage of solid state battery,
It is the key technical problem of solid state battery development.
Patent CN201710833796.2 discloses the inorganic solid electrolyte and its system that a kind of surface is amorphous substance
Preparation Method, comprising the following steps:
A) identical with solid electrolyte basis material chemical component non-using melting-quenching method or high-energy ball milling method preparation
Amorphous material；
B) amorphous substance, binder and solvent are mixed, obtain composite material sizing agent；
C) composite material sizing agent is coated on to the surface of the solid electrolyte basis material, remove solvent and bonding
Agent simultaneously softens the amorphous substance, obtains the inorganic solid electrolyte that surface is amorphous substance.
The patent, will be with basic electrolyte by melting-quenching method or high-energy ball milling method based on oxide electrolyte
The identical oxide of ingredient is prepared into relatively soft amorphous state, and is coated in oxide electrolyte surface.By this method,
Obtain the buffer layer that still there is certain modulus of shearing and flexible relative can preferably be combined with Li cathode.Improve oxide electrolyte
Problem that is unstable with when Li cathode solid-solid contact and contacting difference.
Its existing main problem is:, can be to a certain degree although non-crystal oxide is softer with respect to crystalline oxide
Upper improvement solid-solid contact still based on oxide electrolyte, and carries out surface with the oxide amorphous of homogeneity and is modified
Substantially or oxide, comprehensive performance can be promoted, therefore there are still following in conjunction with the advantages of different electrolyte
Problem:
(1) conductivity of oxide electrolyte is lower, the oxide conductivity after amorphous state also by by certain damage,
Therefore, the electrolytic conductivity that the program obtains is lower compared to traditional oxide electrolyte, solid-state electricity based on this
Energy storage density and the power density performance in pond are poor；
(2) oxide electrolyte matrix is still very rigid, although being coated with one layer of non-crystal oxide in negative side,
It is since the conductivity of non-crystal oxide is lower, reasonable amorphous layer thickness is smaller, can not completely buffer cathode
Volume expansion in charge and discharge process.Meanwhile volume change can also occur in charge and discharge process for anode.Oxide electrolyte
Matrix can not obtain effective solution in charge and discharge process the problem of fragmentation.
Patent CN201580084439.x and document " Cu2ZnSnS4/graphene nanocomposites for
Ultrafast, long life all-solid-state lithium batteries using lithium metal
" etc. anode. files disclose a kind of structure of double-deck sulfide electrolyte, main contents are as follows:
By the Li of high conductivity10GeP2S12With the Li with opposite high stability2S-P2S5-P2O5Laminated construction is prepared into,
Make final battery structure are as follows: anode | Li10GeP2S12|Li2S-P2S5-P2O5| cathode containing Li.
This document passes through in high conductivity Li10GeP2S12Introducing conductivity is slightly lower between cathode containing Li but stability is preferable
Li2S-P2S5-P2O5Layer, improve electrolyte layer to Li stability.
Its existing main problem is: although in high conductance Li10GeP2S12Opposite high stable is introduced between cathode containing Li
The Li of property2S-P2S5-P2O5It can inhibit to a certain extent the interfacial reaction of Li negative side, and retain relatively high conductivity,
But it is same as described above, still there is short slab in comprehensive performance using sulfide merely, the program still has following problems:
(1) sulfide itself flexible relative can preferably be combined with positive and negative anodes, but simultaneously its mechanical strength relative to
Oxide is lower, and in terms of inhibiting Li dendrite, effect is poor compared with oxide；
(2) there are biggish difference in chemical potential between sulfide electrolyte and oxide electrode, therefore, the oxygen with current commercialization
Compound electrode will form very wide Schottky type space charge layer when matching, and cause very big interface impedance, deteriorate solid-state electricity
The performance in pond.
Therefore, current solid electrolyte still needs to improve.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the technological deficiency of background technique, a kind of hybrid solid-state electricity is provided
Solve matter and preparation method thereof.The present invention by sulfide solid electrolyte surface recombination non-crystal oxide solid electrolyte,
Improve the interface problem between sulfide solid electrolyte and electrode material；Meanwhile the present invention is true by thermoforming way
It is compound good to protect heterogeneous interface (oxide/sulfide interface).
It is as follows that the present invention solves technical solution used by above-mentioned technical problem:
A kind of hybrid solid-state electrolyte, the hybrid solid-state electrolyte include at least sulfide solid-state electrolyte layer,
And non-crystal oxide solid-state electrolyte layer.
Preferably, the hybrid solid-state electrolyte is by one layer of sulfide solid-state electrolyte layer and two layers of amorphous state oxygen
Compound solid-state electrolyte layer composition；The non-crystal oxide solid-state electrolyte layer is set to the sulfide solid-state electrolyte layer
Two sides.
Preferably, the hybrid solid-state electrolyte is by one layer of sulfide solid-state electrolyte layer and one layer of amorphous state oxygen
Compound solid-state electrolyte layer composition.
Preferably, the sulfide solid-state electrolyte layer with a thickness of 5~1000 μm, non-crystal oxide solid-state electricity
Solve matter layer with a thickness of 0.1~10 μm.
It is highly preferred that the sulfide solid-state electrolyte layer with a thickness of 10~400 μm, the non-crystal oxide solid-state
Electrolyte layer with a thickness of 0.5~5 μm.
Most preferably, the sulfide solid-state electrolyte layer with a thickness of 20~100 μm, the non-crystal oxide solid-state
Electrolyte layer with a thickness of 0.5~2 μm.
Preferably, the component of the sulfide solid-state electrolyte layer includes sulfide solid electrolyte；The sulfide is solid
State electrolyte includes crystalline state sulfide solid electrolyte or devitrified glass state sulfide solid electrolyte.
It is highly preferred that the crystalline state sulfide solid electrolyte includes the sulfide or Thio- of argyrodite structure
The sulfide of LiSICON structure.
It is further preferred that the sulfide of the argyrodite structure is Li6PS5Cl。
It is further preferred that the sulfide of the Thio-LiSICON structure includes Li10GeP2S12Or it is based on
Li10GeP2S12Carry out the sulfide solid electrolyte obtained after element doping.
It is further preferred that the element of the doping includes Al, Si, Ga, Sn, N, O, Cl, Br, one of I or several
Kind.
It is highly preferred that the devitrified glass state sulfide solid electrolyte includes being based on Li2S-P2S5The sulfide of system or
Based on Li2S-P2S5The sulfide of system carries out the multicomponent system sulfide obtained after element doping.
It is further preferred that the Li2S-P2S5System includes Li2S∶P2S5The sulfide or Li of=70: 30 compositions2S∶
P2S5The sulfide of=75: 25 compositions.
Preferably, the component of the non-crystal oxide solid-state electrolyte layer includes non-crystal oxide solid electrolyte；
The non-crystal oxide solid electrolyte is the oxide lithium ion conductor of amorphous material.
It is highly preferred that the oxide lithium ion conductor includes NASICON structure, perovskite structure, garnet structure
Any one in oxide.
It is further preferred that the oxide of the garnet structure is Li7La3Zr2O12。
Most preferably, the oxide of the garnet structure is Li6.5La3Zr1.5Ta0.5O12。
A kind of hybrid solid-state electrolyte preparation method, which comprises the steps of:
(1) sulfide solid electrolyte is prepared；
(2) non-crystal oxide solid electrolyte is prepared；
(3) by step (1) the sulfide solid electrolyte and step (2) described non-crystal oxide solid electrolyte into
Row is compound, obtains hybrid solid-state electrolyte.
Preferably, in the step (1), the method for preparing sulfide solid electrolyte includes the following steps:
A. ingredient ingredient: is selected according to target sulphide solid electrolyte chemical formula；
B. the ingredient ball milling: is subjected to ball milling；
C. it is heat-treated: the sulfide after the ball milling is heat-treated；
D. it forms: the sulfide after the heat treatment is formed.
Preferably, in the step a, the target sulphide solid electrolyte include crystalline state sulfide solid electrolyte or
Devitrified glass state sulfide solid electrolyte.
It is highly preferred that the crystalline state sulfide solid electrolyte includes the sulfide or Thio- of argyrodite structure
The sulfide of LiSICON structure.
It is further preferred that the sulfide of the argyrodite structure is Li6PS5Cl。
It is further preferred that the sulfide of the Thio-LiSICON structure includes Li10GeP2S12Or it is based on
Li10GeP2S12Carry out the sulfide solid electrolyte obtained after element doping.
It is further preferred that the element of the doping includes Al, Si, Ga, Sn, N, O, Cl, Br, one of I or several
Kind.
It is highly preferred that the devitrified glass state sulfide solid electrolyte includes being based on Li2S-P2S5The sulfide of system or
Based on Li2S-P2S5The sulfide of system carries out the multicomponent system sulfide obtained after element doping.
It is further preferred that the Li2S-P2S5System includes Li2S∶P2S5The sulfide or Li of=70: 30 compositions2S∶
P2SsThe sulfide of=75: 25 compositions.
Preferably, in the step b, the ball milling method includes high-energy ball milling, any one in vibratory milling.
Preferably, in the step b, the ratio of grinding media to material when ball milling is ball: material=(10~50): 1.
It is highly preferred that in the step b, the ratio of grinding media to material when ball milling is ball: material=(20~30): 1.
Preferably, in the step b, the revolving speed when ball milling is 200~700r/min.
It is highly preferred that in the step b, the revolving speed when ball milling is 300~600r/min.
Preferably, in the step b, the Ball-milling Time is >=4h.
It is highly preferred that the Ball-milling Time is 8~48h in the step b.
Most preferably, in the step b, the Ball-milling Time is 12~36h.
Preferably, in the step b, the mechanical milling process is continuous or interval.
Preferably, in the step c, the temperature of the heat treatment is 200~800 DEG C, and the time is >=30min.
It is highly preferred that the temperature of the heat treatment is 300~700 DEG C in the step c, the time is 4~12h.
Preferably, in the step d, the forming method includes cold pressing, hot pressing, or after mixing with binder, solvent
Using any one forming method in curtain coating, casting, spin coating method.
It is highly preferred that the forming method is cold-press method in the step d；The cold-press method includes the following steps:
The sulfide powders for weighing certain mass, pressure maintaining 2min obtains electrolyte sheet under the pressure of 20MPa.
It is highly preferred that the forming method is the tape casting in the step d；The tape casting includes the following steps:
Sulfide solid electrolyte powder is mixed with 8: 1: 1 with binder and solvent after sizing mixing, is applied to the tape casting
On PET film, dielectric film is removed after dry, in 260 DEG C of (75Li2S-25P2S5) it is heat-treated 3h, PVDF is discharged simultaneously in controlled micro crystallization,
Obtain fine and close sulfide film.
Preferably, the binder is PVDF.
Preferably, the solvent is NMP.
Preferably, in the step (2), the method for preparing sulfide solid electrolyte includes melting-quenching method, height
It can ball-milling method, hydro-thermal method, microemulsion method, any one in magnetron sputtering deposition method.
It is highly preferred that the method for preparing non-crystal oxide solid electrolyte is to melt-quench in the step (2)
Cold process includes the following steps:
A. ingredient, mixing ingredient: are selected according to target non-crystal oxide solid electrolyte chemical formula；
B. melting-quenching: the powder mixed is kept the temperature, quenching is carried out after heat preservation, obtains amorphous state oxygen
Compound solid electrolyte；
C. it crushes: the non-crystal oxide solid electrolyte being crushed, non-crystal oxide solid electrolyte powder is obtained；
D. it sizes mixing: the non-crystal oxide solid electrolyte powder being mixed with binder and solvent and is sized mixing, amorphous is obtained
State oxide solid electrolyte slurry；
Preferably, in the step a, the target non-crystal oxide solid electrolyte is the oxide lithium of amorphous material
Ion conductor.
It is highly preferred that the oxide lithium ion conductor includes NASICON structure, perovskite structure, garnet structure
Any one in oxide.
It is further preferred that the oxide of the garnet structure is Li7La3Zr2O12。
Most preferably, the oxide of the garnet structure is Li6.5La3Zr1.5Ta0.5O12。
Preferably, in the step a, the hybrid mode is hybrid mode generally known in the art.
Preferably, in the step b, the temperature of the heat preservation is 1500~1800 DEG C, the time is 1~for 24 hours.
It is highly preferred that the temperature of the heat preservation is 1600~1700 DEG C in the step b, the time is 5~10h.
Preferably, in the step b, the medium when quenching includes liquid nitrogen, oil, water, appointing in inorganic salt solution
It anticipates one kind.
It is furthermore preferred that in the step b, the medium when quenching is liquid nitrogen.
Preferably, in the step d, the binder and the solvent are selected from the common binder and solvent in this field.
It is highly preferred that the method for preparing non-crystal oxide solid electrolyte is high-energy ball milling in the step (2)
Method；The high-energy ball milling method uses the high-energy ball milling method as disclosed in patent CN201710833796.2.
It is highly preferred that the method for preparing non-crystal oxide solid electrolyte is hydro-thermal method in the step (2)；
The hydro-thermal method uses the hydro-thermal method as disclosed in patent CN201310698212.7.
It is highly preferred that the method for preparing non-crystal oxide solid electrolyte is microemulsion in the step (2)
Method；The microemulsion method uses the microemulsion method as disclosed in patent CN201810259936.4.
It is highly preferred that the method for preparing non-crystal oxide solid electrolyte is magnetron sputtering in the step (2)
Sedimentation；The magnetron sputtering deposition method uses the magnetron sputtering deposition method as disclosed in CN200710039147.1.
Preferably, in the step (3), the complex method includes pressure sintering, discharge plasma sintering method, vacuum sputtering
Method, vacuum vapour deposition, any one in chemical vapour deposition technique.
It is highly preferred that the complex method is pressure sintering in the step (3), include the following steps:
A. it coats: the non-crystal oxide solid electrolyte slurry is coated to the sulfide solid electrolyte matrix
Surface, the solid electrolyte after must coating；
B. it dries: the hybrid solid-state electrolyte after the coating is dried, the solid electrolyte after must drying；
C. hot pressing: the solid electrolyte after the drying is subjected to hot-pressing processing, obtains hybrid solid-state electrolyte.
Preferably, in the step a, the method that when coating uses is in curtain coating, blade coating, spraying, silk-screen printing
Any one.
Preferably, described applied to single side coating or dual coating in the step a.
Preferably, in the step a, the coat thickness are as follows: 0.1 μm≤coat thickness≤10 μm.
It is highly preferred that in the step a, the coat thickness are as follows: 0.5 μm≤coat thickness≤5 μm.
Most preferably, in the step a, the coat thickness are as follows: 0.5 μm≤coat thickness≤2 μm.
Preferably, in the step a, the thickness of the sulfide solid electrolyte matrix are as follows: 5 μm≤sulfide solid-state electricity
Solve matter matrix≤1000 μm.
It is highly preferred that in the step a, the thickness of the sulfide solid electrolyte matrix are as follows: 10 μm≤sulfide is solid
State electrolyte matrix≤400 μm.
Most preferably, in the step a, the thickness of the sulfide solid electrolyte matrix are as follows: 20 μm≤sulfide is solid
State electrolyte matrix≤100 μm.
Preferably, in the step c, the pressure when hot-pressing processing is 10~300MPa.
It is highly preferred that in the step c, the pressure when hot-pressing processing is 20~200MPa.
Preferably, in the step c, the heating temperature when hot-pressing processing is 150~600 DEG C.
It is highly preferred that in the step c, the heating temperature when hot-pressing processing is 250~500 DEG C.
Preferably, in the step c, the time of the hot-pressing processing is >=10min.
It is highly preferred that the time of the hot-pressing processing is 30min~10h in the step c.
It, will be non-while softening surface amorphous oxide solid-state electrolyte layer by hot pressing in above-mentioned technical proposal
Crystalline oxide solid-state electrolyte layer and sulfide solid-state electrolyte layer good combination, avoid the occurrence of out-phase structure in subsequent processing
The case where with being mutually disengaged in use process；The hot pressing can be the closed pressurization using mold.
It is highly preferred that the complex method is discharge plasma sintering method in the step (3)；The plasma discharging
Sintering process uses the discharge plasma sintering method as disclosed in patent CN200710177048.X, specific as follows:
A. by step (2) the non-crystal oxide solid electrolyte powder-step (1) sulfide solid electrolyte
Powder-step (2) the non-crystal oxide solid electrolyte powder (such as single layer processing can cancel the side) is with 1: (20~200)
: 1 ratio is packed into sintering grinding tool；
B. 1~10min is handled at 200~600 DEG C, heating rate is 20~100 DEG C/min, sintering pressure 500MPa
~1GPa, sintering atmosphere are vacuum or Ar gas shielded；
C. 2~5h is heat-treated in dry air atmosphere at 200~400 DEG C.
In above-mentioned technical proposal, the vacuum sputtering, the vacuum vapour deposition and described chemical vapour deposition technique etc. are originally
The common vapour deposition process of area research personnel is relatively inefficient, but can prepare the accurate controllable compound thin layer of thickness,
And guarantee that biphase interface is well combined.
In above-mentioned technical proposal, the step (1) and the step (3) carry out in the atmosphere of strict control moisture.
A kind of solid state battery, including hybrid solid-state electrolyte as described above.
Basic principle of the invention:
(1) non-crystal oxide is higher than the modulus of shearing of sulfide, therefore, coats amorphous state in sulfide bath surface
Oxide can be effectively improved the inhibiting effect to Li dendrite；
(2) sulfide ionic conductivity itself is very high；Meanwhile sulfide itself is very soft, therefore to electrode in charge and discharge
Volume change in journey has stronger tolerance；To the non-crystal oxide solid-state of low ionic conductivity in the structure
The thickness requirements of electrolyte layer are lower, and the conductivity of electrolyte entirety is then made to be protected；
(3) between sulfide and Li cathode be inserted into one layer of non-crystal oxide solid-state electrolyte layer, can to avoid Li with
The direct contact of sulfide, to avoid Li to Ge in sulfide electrolyte4+The reduction of equal elements, and then avoid electrolyte performance
Deterioration；
(4) non-crystal oxide relative to crystalline oxide electrolyte want it is soft (but still maintain certain modulus of shearing,
It is enough to inhibit Li dendrite, this is the reason of not selecting sulfide and polymer to be coated), it therefore, can when being contacted with electrode
To provide relatively good contact interface, the solid-solid that crystalline oxide generates between electrode since itself is too hard is avoided the occurrence of
The problem of poor contact；Meanwhile amorphous substance without grain boundary features can avoid the occurrence of the feelings that Li dendrite is grown in crystal boundary
Condition；
(5) the non-crystal oxide solid-state electrolyte layer that diversion but non-conductive son are introduced in side of the positive electrode, can inhibit sulphur
The growth of compound/oxide interface space charge layer and form wide Schottky type space charge layer, to avoid big boundary
The generation of surface resistance, thus allow the sulfide electrolyte of the structure directly with the ternary material of current commercialization, ferric phosphate
The positive electrodes such as lithium, cobalt acid lithium match.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention use the sulfide solid electrolyte of high conductance for matrix, in conjunction with with respect to high shear modulus and
The non-crystal oxide solid electrolyte thin layer of interface stability, ensure conductivity and electrolyte/electrode it is good it is accessible before
Put: a. improves the inhibition to Li dendrite in negative side；B. the non-crystal oxide of sub in side of the positive electrode diversion and non-conductive son is solid
State electrolyte layer can effectively inhibit the growth of space charge layer, reduce interface impedance；
(2) present invention is using the sulfide solid electrolyte of flexible relative as matrix, to anode and cathode in charge and discharge process
In volume change have better tolerance；
(3) present invention is due to being Heterogeneous Composite, and oxide is different with the thermal capacitance and coefficient of thermal expansion of sulfide, in heat treatment
It is easy to happen interface mismatch, leads to modified failure；Therefore, in the present invention, using hot pressing means, keep during heat treatment
External pressure, to guarantee the good compound of heterojunction structure.
Detailed description of the invention
Fig. 1 is a kind of structure chart of hybrid solid-state electrolyte of the present invention；
Fig. 2 is another structure chart of hybrid solid-state electrolyte of the present invention；
Fig. 3 is hybrid solid-state electrolyte preparation flow figure of the present invention.
The corresponding component names of each appended drawing reference are in figure:
1- sulfide solid-state electrolyte layer；2- non-crystal oxide solid-state electrolyte layer.
Specific embodiment
In order to better understand the content of the present invention, it is described further combined with specific embodiments below with attached drawing.Ying Li
Solution, these embodiments are only used for that the present invention is further described, rather than limit the scope of the invention.In addition, it should also be understood that,
After having read content of the present invention, person skilled in art makes some nonessential changes or adjustment to the present invention,
Still fall within protection scope of the present invention.
Term of the present invention is explained:
Coating: substance A is covered on substance B surface in the form of thin layer/film using certain method.
Hot pressing: apply certain pressure while heat treatment.
Heterogeneous interface: the different interface of the substance and phase structure at both ends (in turn, homogeneity, that is, substance is identical).
Ionic conductivity: the non-electronic conductivity that electrical transmission is carried out for carrier with ion (lithium ion)；It is described in text
Conductivity, if plus illustrate refer to be all ionic conductivity.
Space charge layer: it is originated from semiconductor PN concept and refers to herein due to being deposited between sulfide and oxide
In biggish difference in chemical potential, Li ion spontaneous can be migrated from sulfide to oxide, to form the poor region Li in sulfide side.
Due to poor Li, ionic conductivity is very low in the region.Simultaneously as oxide electrode is electron-ion mixed conductor, enrichment
Li+Ion, can by external circuit electronics neutralize (built in field can not be formed), therefore the Li ion in sulfide can continue to
Migration is in oxide to form the very wide poor area Li, the space charge layer of this form, also known as Schottky type space electricity
Lotus layer.
Oxide lithium ion conductor: can be with the oxide solid state medium of conducting lithium ions, Wen Zhongsuo under the conditions of charge and discharge
Stating oxide solid electrolyte is also the same meaning.The concept of sulfide solid electrolyte described in text is similar, material
Main body is changed to sulfide.
Embodiment 1
A kind of hybrid solid-state electrolyte, the hybrid solid-state electrolyte are included at least by sulfide solid electrolyte group
At sulfide solid-state electrolyte layer 1 and the non-crystal oxide solid-state electricity that is made of non-crystal oxide solid electrolyte
Solve matter layer 2.
The present embodiment is by improving sulphur in sulfide solid electrolyte surface recombination non-crystal oxide solid electrolyte
Interface problem between compound solid electrolyte and electrode material.
Embodiment 2
The present embodiment is advanced optimized on the basis of embodiment 1, as shown in Figure 1, the hybrid solid-state is electrolysed
Matter is made of one layer of sulfide solid-state electrolyte layer 1 and two layers of non-crystal oxide solid-state electrolyte layer 2；The amorphous state
Oxide solid-state electrolyte layer 1 is set to 2 two sides of sulfide solid-state electrolyte layer.
When just extremely oxide, the cathode of solid state battery are lithium, using the compound of double-layer structure described in the present embodiment
Solid electrolyte.
Embodiment 3
The present embodiment is advanced optimized on the basis of embodiment 1, as shown in Fig. 2, the hybrid solid-state is electrolysed
Matter forms 2 by one layer of sulfide solid-state electrolyte layer 1 and one layer of non-crystal oxide solid-state electrolyte layer.
When the just extremely sulfide, such as nickel sulfide of solid state battery, when cathode is lithium, using side of the positive electrode described in the present embodiment without
The single layer structure hybrid solid-state of non-crystal oxide solid-state electrolyte layer, negative side tool non-crystal oxide solid-state electrolyte layer
Electrolyte；When the just extremely oxide of solid state battery, when cathode is graphite, using the tool amorphous state oxidation of side of the positive electrode described in embodiment
The single layer structure hybrid solid-state electrolyte of object solid-state electrolyte layer, negative side without non-crystal oxide solid-state electrolyte layer.
Embodiment 4
The present embodiment is advanced optimized on the basis of embodiment 2 and embodiment 3, the sulfide solid electrolyte
Layer 1 with a thickness of 5~1000 μm, the non-crystal oxide solid-state electrolyte layer 2 with a thickness of 0.1~10 μm；Above-mentioned thickness
For the thickness limit of hybrid solid-state electrolyte of the present invention.
The sulfide solid-state electrolyte layer 1 with a thickness of 10~400 μm, the non-crystal oxide solid-state electrolyte layer
2 with a thickness of 0.5~5 μm；The hybrid solid-state electrolyte preparation of above-mentioned thickness is the easiest.
The sulfide solid-state electrolyte layer 1 with a thickness of 20~100 μm, the non-crystal oxide solid-state electrolyte layer
2 with a thickness of 0.5~2 μm；The hybrid solid-state electrolyte performance of above-mentioned thickness is optimal.
The thickness of the sulfide solid-state electrolyte layer 1 and the thickness of the non-crystal oxide solid-state electrolyte layer 2
Selection is ionic conductivity based on solid electrolyte and structural stability and makes.
The component of the sulfide solid-state electrolyte layer 1 includes sulfide solid electrolyte；The sulfide solid state electrolysis
Matter includes crystalline state sulfide solid electrolyte or devitrified glass state sulfide solid electrolyte.
The crystalline state sulfide solid electrolyte includes the sulfide or Thio-LiSICON structure of argyrodite structure
Sulfide.
The sulfide of the argyrodite structure is Li6PS5Cl。
The sulfide of the Thio-LiSICON structure includes Li10GeP2S12Or it is based on Li10GeP2S12Carry out element doping
The sulfide solid electrolyte obtained afterwards.
The element of the doping includes Al, Si, Ga, Sn, N, O, Cl, Br, one or more of I.
The devitrified glass state sulfide solid electrolyte includes being based on Li2S-P2S5The sulfide of system is based on Li2S-
P2S5The sulfide of system carries out the multicomponent system sulfide obtained after element doping.
The Li2S-P2S5System includes Li2S∶P2S5The sulfide or Li of=70: 30 compositions2S∶P2S5=75: 25 compositions
Sulfide.
The component of the non-crystal oxide solid-state electrolyte layer 2 includes non-crystal oxide solid electrolyte；It is described non-
Crystalline oxide solid electrolyte is the oxide lithium ion conductor of amorphous material.
The oxide lithium ion conductor include NASICON structure, perovskite structure, garnet structure oxide in
Any one.
The oxide of the garnet structure is Li7La3Zr2O12。
The oxide of the garnet structure is Li6.5La3Zr1.5Ta0.5O12。
The present embodiment uses the sulfide solid electrolyte of high conductance for matrix, in conjunction with opposite high shear modulus and boundary
The non-crystal oxide solid electrolyte thin layer of face stability is ensuring conductivity and the good accessible premise of electrolyte/electrode
Under: a. improves the inhibition to Li dendrite in negative side；B. in the non-crystal oxide solid-state of side of the positive electrode diversion and non-conductive son
Electrolyte layer can effectively inhibit the growth of space charge layer, reduce interface impedance；
Meanwhile the present embodiment is using the sulfide solid electrolyte of flexible relative as matrix, to anode and cathode in charge and discharge
Volume change in the process has better tolerance.
Embodiment 5
By Li2S, GeS2And P2S5By 5: 1: 1 molar ratio weighing, it is encapsulated into ball grinder by ratio of grinding media to material 30: 1, with 550rpm
Revolving speed ball milling 8h after, take out, grinding distribution after scraper, Reseal into tank, continue ball milling 8h.After the powder tabletting of acquisition
It is heat-treated 8h at 700 DEG C, then grinds, obtains Li10GeP2S12Powder.The powder of acquisition is pushed in 100MPa pressure
Piece obtains sulfide matrix.
By Li2CO3, La2O3And ZrO2Stoichiometrically Li7La3Zr2O12After weighing, with the revolving speed ball milling of 400rpm
24h.After the powder of acquisition is kept the temperature 8h at 1600 DEG C, liquid nitrogen quenching is poured into.The non-crystal oxide that quenching is obtained crushes
And further ball milling 12h obtains non-crystal oxide powder at 550rpm.By the powder and PVDF, NMP with 7: 2: 1 ratio
After mixing is sized mixing, blade coating arrives sulfide matrix both side surface, dries in 80 DEG C of vacuum drying ovens.
Obtained composite electrolyte is obtained into the good combined electrolysis of interfacial contact at 450 DEG C with 120Mpa hot pressing 3h
Matter.Wherein for sulfide electrolyte layer with a thickness of 200 μm, non-crystal oxide layer is obstruction electricity with stainless steel with a thickness of 2.4 μm
Pole, it is 3.8 × 10 that test, which obtains conductivity at room temperature,-3S/cm.With LiCoO2For anode, Li piece is cathode, and test is put
Electric specific capacity is 124mAh/g, after 0.1C is recycled 50 weeks, capacity retention ratio 95.5%.
Embodiment 6
By Li2S, GeS2And P2S5By 5: 1: 1 molar ratio weighing, it is encapsulated into ball grinder by ratio of grinding media to material 30: 1, with 550rpm
Revolving speed ball milling 8h after, take out, grinding distribution after scraper, Reseal into tank, continue ball milling 8h.After the powder tabletting of acquisition
It is heat-treated 8h at 700 DEG C, then grinds, obtains Li10GeP2S12Powder.In mass ratio 8: 1: 1 weigh Li10GeP2S12,
PVDF and NMP mixing size mixing, by the tape casting by the slurry coating of acquisition on a pet film, removed after drying, obtain
Li10GeP2S12Film.
By Li2CO3, La2O3, ZrO2And Ta2O5Stoichiometrically Li6.5La3Zr1.5Ta0.5O12After weighing, with 400rpm
Revolving speed ball milling for 24 hours.After the powder of acquisition is kept the temperature 8h at 1600 DEG C, liquid nitrogen quenching is poured into.The amorphous state that quenching is obtained
Oxide crushes the step ball milling 12h at 550rpm that goes forward side by side and obtains non-crystal oxide powder.By the powder and PVDF, NMP with 8
: after 1: 1 ratio mixing is sized mixing, Li is coated to by the tape casting10GeP2S12On film, dried in 80 DEG C of vacuum drying ovens.
Obtained composite electrolyte is obtained into the good combined electrolysis of interfacial contact at 500 DEG C with 150Mpa hot pressing 2h
Matter.Wherein sulfide electrolyte layer is with a thickness of 50 μm, and non-crystal oxide layer is with a thickness of 1.0 μm, using stainless steel as blocking electrode,
It is 5.3 × 10 that test, which obtains conductivity at room temperature,-3S/cm.With LiCoO2For anode, Li piece is cathode, and test obtains electric discharge ratio
Capacity is 135mAh/g, after 0.1C is recycled 50 weeks, capacity retention ratio 97.6%.
Embodiment 7
By Li2S, P2S5By 70: 30 molar ratio weighing, it is encapsulated into ball grinder by ratio of grinding media to material 25: 1, with the revolving speed of 400rpm
Ball milling for 24 hours after.The powder of acquisition is heat-treated 2h at 260 DEG C, obtains Li7P3S11Powder.By Li7P3S11Powder is in 100MPa
Lower sheeting obtains sulfide electrolyte matrix.
By Li2CO3, La2O3And ZrO2Stoichiometrically Li7La3Zr2O12After weighing, with the revolving speed ball milling of 500rpm
24h.After the powder of acquisition is kept the temperature 12h at 1700 DEG C, liquid nitrogen quenching is poured into.The non-crystal oxide that quenching is obtained crushes
And further ball milling 12h obtains non-crystal oxide powder at 550rpm.By the powder and PVB, toluene with 8: 2: 1 ratio
After mixing is sized mixing, blade coating arrives sulfide matrix both side surface, dries in 80 DEG C of vacuum drying ovens.
Obtained composite electrolyte is obtained into the good combined electrolysis of interfacial contact at 300 DEG C with 200Mpa hot pressing 5h
Matter.Wherein for sulfide electrolyte layer with a thickness of 100 μm, non-crystal oxide layer is obstruction electricity with stainless steel with a thickness of 2.2 μm
Pole, it is 2.6 × 10 that test, which obtains conductivity at room temperature,-3S/cm.With LiCoO2For anode, Li piece is cathode, and test is put
Electric specific capacity is 122mAh/g, after 0.1C is recycled 50 weeks, capacity retention ratio 94.3%.
Embodiment 8
By Li2S, P2S5By 75: 25 molar ratio weighing, it is encapsulated into ball grinder by ratio of grinding media to material 20: 1, with the revolving speed of 500rpm
After ball milling 18h.The powder of acquisition is heat-treated 4h at 250 DEG C, obtains β-Li3PS4Powder.By β-Li3PS4Powder exists
100MPa lower sheeting obtains sulfide electrolyte matrix.
By Li2CO3, La2O3, ZrO2And Ta2O5Stoichiometrically Li6.4La3Zr1.4Ta0.6O12After weighing, with 500rpm
Revolving speed ball milling 20h.After the powder of acquisition is kept the temperature 15h at 1650 DEG C, liquid nitrogen quenching is poured into.The amorphous state that quenching is obtained
Oxide crushes the step ball milling 12h at 550rpm that goes forward side by side and obtains non-crystal oxide powder.By the powder and PVDF, NMP with 8
: after 2: 1 ratio mixing is sized mixing, sulfide matrix surface is sprayed to, is dried in 80 DEG C of vacuum drying ovens.
Obtained composite electrolyte is obtained into the good combined electrolysis of interfacial contact at 270 DEG C with 200Mpa hot pressing 5h
Matter.Wherein for sulfide electrolyte layer with a thickness of 200 μm, non-crystal oxide layer is obstruction electricity with stainless steel with a thickness of 2.6 μm
Pole, it is 2.3 × 10 that test, which obtains conductivity at room temperature,-3S/cm.With LiCoO2For anode, Li piece is cathode, and test is put
Electric specific capacity is 119mAh/g, and 0.51 circulation is after 50 weeks, capacity retention ratio 94.9%.
Comparative example 1
By Li2CO3, La2O3, ZrO2And Ta2O5Stoichiometrically Li6.5La3Zr1.5Ta0.5O12After weighing, with 400rpm
Revolving speed ball milling for 24 hours.After the powder of acquisition is kept the temperature 6h at 1100 DEG C, furnace cooling obtains Li6.5La3Zr1.5Ta0.5O12Powder
End.Above-mentioned powder is mixed with PVDF and NMP with 8: 1: 1 mass ratioes and is sized mixing, by the tape casting by the slurry coating of acquisition in PET
It on film, is removed after drying, obtains Li6.5La3Zr1.5Ta0.5O12Film；Li6.5La3Zr1.5Ta0.5O12Crystalline film is with a thickness of 50 μ
m。
Amorphous state Li6.5La3Zr1.5Ta0.5O12Preparation method is as described in Example 6, amorphous state Li6.5La3Zr1.5Ta0.5O12
Layer is with a thickness of 1.0 μm.
Using stainless steel as blocking electrode, it is 3.3 × 10 that test, which obtains conductivity at room temperature,-4S/cm.With LiCoO2It is positive
Pole, Li piece are cathode, and it is 112mAh/g that test, which obtains specific discharge capacity, after 0.1C is recycled 50 weeks, capacity retention ratio 78.4%.
Comparative example 2
Li is prepared according to preparation method described in embodiment 610GeP2S12Film.
By Li2CO3, La2O3, ZrO2And Ta2O5Stoichiometrically Li6.5La3Zr1.5Ta0.5O12After weighing, with 400rpm
Revolving speed ball milling for 24 hours.After the powder of acquisition is kept the temperature 6h at 1100 DEG C, furnace cooling obtains crystalline state
Li6.5La3Zr1.5Ta0.5O12Powder.After above-mentioned powder and PVDF, NMP are sized mixing with 8: 1: 1 ratio mixing, pass through the tape casting
It is coated to Li10GeP2S12On film, dried in 80 DEG C of vacuum drying ovens.
Obtained composite electrolyte is obtained into the good combined electrolysis of interfacial contact at 500 DEG C with 150Mpa hot pressing 2h
Matter.Wherein sulfide electrolyte layer is with a thickness of 50 μm, and crystalline oxide layer is with a thickness of 1.0 μm, using stainless steel as blocking electrode, surveys
It is 5.4 × 10 that examination, which obtains conductivity at room temperature,-3S/cm.With LiCoO2For anode, Li piece is cathode, and test obtains electric discharge specific volume
Amount is 134mAh/g, after 0.1C is recycled 50 weeks, capacity retention ratio 37.6%.
Comparative example 1 is compound by crystalline oxide solid electrolyte and the progress of non-crystal oxide solid electrolyte, resulting
The ionic conductivity of hybrid solid-state electrolyte, which is compared, of the present invention uses sulfide solid electrolyte for the compound of matrix
Solid electrolyte wants low, while capacity retention ratio also wants low.
Comparative example 2 is compound by sulfide solid electrolyte and the progress of crystalline oxide solid electrolyte, resulting compound
Although solid electrolyte can obtain relatively high ionic conductivity, promotion is limited, in cyclic process, due to crystalline state
Oxide coating quality is harder, is easy to generate crack in electrode/electrolyte interface and oxide/sulfide interface, causes to hold
Amount generates the decline of cliff of displacement formula.
Above description is not limitation of the present invention, and the present invention is also not limited to the example above.The art it is common
Within the essential scope of the present invention, the variations, modifications, additions or substitutions made also should belong to protection of the invention to technical staff
Range.
Claims (10)
1. a kind of hybrid solid-state electrolyte, which is characterized in that the hybrid solid-state electrolyte includes at least sulfide solid-state
Electrolyte layer (1) and non-crystal oxide solid-state electrolyte layer (2).
2. a kind of hybrid solid-state electrolyte as described in claim 1, which is characterized in that the hybrid solid-state electrolyte by
One layer of sulfide solid-state electrolyte layer (1) and two layers of non-crystal oxide solid-state electrolyte layer (2) composition；The amorphous state
Oxide solid-state electrolyte layer (1) is set to sulfide solid-state electrolyte layer (2) two sides.
3. a kind of hybrid solid-state electrolyte as described in claim 1, which is characterized in that the hybrid solid-state electrolyte by
One layer of sulfide solid-state electrolyte layer (1) and one layer of non-crystal oxide solid-state electrolyte layer composition (2).
4. a kind of hybrid solid-state electrolyte as described in claim 1, which is characterized in that the sulfide solid-state electrolyte layer
(1) with a thickness of 5~1000 μm, the non-crystal oxide solid-state electrolyte layer (2) with a thickness of 0.1~10 μm.
5. a kind of hybrid solid-state electrolyte as described in claim 1, which is characterized in that the sulfide solid-state electrolyte layer
(1) component includes sulfide solid electrolyte；The sulfide solid electrolyte include crystalline state sulfide solid electrolyte or
Devitrified glass state sulfide solid electrolyte；The crystalline state sulfide solid electrolyte include argyrodite structure sulfide or
The sulfide of Thio-LiSICON structure；The devitrified glass state sulfide solid electrolyte includes being based on Li2S-P2S5System
Sulfide is based on Li2S-P2S5The sulfide of system carries out the multicomponent system sulfide obtained after element doping.
6. a kind of hybrid solid-state electrolyte as claimed in claim 5, which is characterized in that the Thio-LiSICON structure
Sulfide includes Li10GeP2S12Or it is based on Li10GeP2S12Carry out the sulfide solid electrolyte obtained after element doping.
7. a kind of hybrid solid-state electrolyte as described in claim 1, which is characterized in that the non-crystal oxide solid-state electricity
The component for solving matter layer (2) includes non-crystal oxide solid electrolyte；The non-crystal oxide solid electrolyte is amorphous state
The oxide lithium ion conductor of change；The oxide lithium ion conductor includes NASICON structure, perovskite structure, garnet knot
Any one in the oxide of structure.
8. a kind of hybrid solid-state electrolyte as claimed in claim 7, which is characterized in that the oxide of the garnet structure
For Li6.5La3Zr1.5Ta0.5O12。
9. a kind of hybrid solid-state electrolyte preparation method, which comprises the steps of:
(1) sulfide solid electrolyte is prepared；
(2) non-crystal oxide solid electrolyte is prepared；
(3) step (1) the sulfide solid electrolyte and step (2) described non-crystal oxide solid electrolyte are answered
It closes, obtains hybrid solid-state electrolyte.
10. a kind of hybrid solid-state electrolyte preparation method as claimed in claim 9, which is characterized in that the step (1)
In, the method for preparing sulfide solid electrolyte includes the following steps:
A. ingredient ingredient: is selected according to target sulphide solid electrolyte chemical formula；
B. the ingredient ball milling: is subjected to ball milling；
C. it is heat-treated: the sulfide after the ball milling is heat-treated；
D. it forms: the sulfide after the heat treatment is formed；
In the step (2), the method for preparing non-crystal oxide solid electrolyte is melting-quenching method, including as follows
Step:
A. ingredient, mixing ingredient: are selected according to target non-crystal oxide solid electrolyte chemical formula；
B. melting-quenching: the powder mixed is kept the temperature, quenching is carried out after heat preservation, obtains non-crystal oxide
Solid electrolyte；
C. it crushes: the non-crystal oxide solid electrolyte being crushed, non-crystal oxide solid electrolyte powder is obtained；
D. it sizes mixing: the non-crystal oxide solid electrolyte powder being mixed with binder and solvent and is sized mixing, amorphous state oxygen is obtained
Compound solid electrolyte slurry；
In the step (3), the complex method is pressure sintering, is included the following steps:
A. it coats: the non-crystal oxide solid electrolyte slurry is coated to the sulfide solid electrolyte matrix table
Face, the solid electrolyte after must coating；
B. it dries: the solid electrolyte after the coating is dried, the solid electrolyte after must drying；
C. hot pressing: the solid electrolyte after the drying is subjected to hot-pressing processing, obtains hybrid solid-state electrolyte.
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| CN113745651A (en) * | 2021-08-27 | 2021-12-03 | 深圳市研一新材料有限责任公司 | Coated sulfide solid electrolyte and preparation method and application thereof |
| CN113745651B (en) * | 2021-08-27 | 2023-12-05 | 深圳市研一新材料有限责任公司 | Coated sulfide solid electrolyte and preparation method and application thereof |
| WO2023120978A1 (en) * | 2021-12-22 | 2023-06-29 | 한국과학기술연구원 | Method for manufacturing composite solid electrolyte sheet |
| CN114421004A (en) * | 2022-01-24 | 2022-04-29 | 蜂巢能源科技(无锡)有限公司 | Sulfide solid electrolyte and preparation method and application thereof |
| CN114421004B (en) * | 2022-01-24 | 2023-09-19 | 蜂巢能源科技(无锡)有限公司 | Sulfide solid electrolyte and preparation method and application thereof |
| CN115360320A (en) * | 2022-10-19 | 2022-11-18 | 中国科学院精密测量科学与技术创新研究院 | All-solid-state battery with low interface resistance and high lithium metal stability and preparation method thereof |
| CN118299652A (en) * | 2024-06-04 | 2024-07-05 | 上海屹锂新能源科技有限公司 | Heterojunction solid electrolyte and preparation method thereof |
| CN118299652B (en) * | 2024-06-04 | 2024-09-24 | 上海屹锂新能源科技有限公司 | Heterojunction solid electrolyte and preparation method thereof |
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