CN101040401A - Lithium ion secondary battery and a solid electrolyte thereof - Google Patents

Lithium ion secondary battery and a solid electrolyte thereof Download PDF

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CN101040401A
CN101040401A CNA2005800352315A CN200580035231A CN101040401A CN 101040401 A CN101040401 A CN 101040401A CN A2005800352315 A CNA2005800352315 A CN A2005800352315A CN 200580035231 A CN200580035231 A CN 200580035231A CN 101040401 A CN101040401 A CN 101040401A
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solid electrolyte
lithium ion
ion conducting
positive electrode
negative electrode
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印田靖
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Ohara Inc
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Ohara Inc
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/10—Energy storage using batteries

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Abstract

A solid electrolyte comprising powder of an inorganic substance comprising a lithium ion conductive crystal or powder of a lithium ion conductive glass-ceramic and an organic polymer added with an inorganic or organic lithium salt, and being free of an electrolytic solution. The organic polymer is a copolymer, a bridge structure or a mixture thereof of polyethylene oxide and other organic polymer or polymers. A lithium ion secondary battery comprises this solid electrolyte.

Description

Lithium rechargeable battery and solid electrolyte thereof
Technical field
The present invention relates to a kind of lithium rechargeable battery that mainly is suitable for the solid electrolyte of lithium rechargeable battery and comprises this solid electrolyte.
Background technology
In the past, wherein microporous membrane (being called as spacer) generally is used as the used electrolyte of lithium rechargeable battery with the electrolyte of non aqueous electrolysis solution impregnation.The lithium rechargeable battery (polymer battery) of the polymer dielectric that use is made up of polymer recently Billy with the more attentions of electrolytical battery attraction of this use electrolytic solution.4
This polymer battery uses the gel type electrolyte, and wherein polymer is with the impregnation of liquid electrolytic solution.Because electrolytic solution remains in the polymer, so battery has the very little advantage of leak of liquid possibility and battery security thereby is improved, and battery has an improvement degree of freedom in shape what battery can present in addition.
Because such polymer dielectric has the lithium ion conducting rate lower than the electrolyte of electrolytic solution type, so attempted reducing the thickness of this polymer dielectric.Yet under the situation of the thickness that reduces polymer dielectric, its mechanical strength also reduces, and result's polymer dielectric during it is made is damaged and its positive electrode and negative electrode are short-circuited.
Japan Patent is openly speciallyyed permit the spy and is opened flat 6-140052 and proposed a kind of by inorganic oxide such as aluminium oxide are added in the electrolyte to improve the prepared solid electrolyte of its mechanical strength.Outside the alumina, described inorganic oxide also comprises silicon dioxide and lithium aluminate.
Yet, to can cause the significantly reduced problem of lithium ion conducting rate in the solid electrolyte in inorganic compound (for example aluminium oxide) the adding electrolyte, in addition, when charging repeatedly in the lithium rechargeable battery with this solid electrolyte and discharging, electrolyte and inorganic oxide react, thereby cause the remarkable decline of the charge-discharge cycles feature of lithium rechargeable battery.
The open case of Japanese Patent Laid proposes for 2004-185862 number a kind of by the prepared lithium rechargeable battery of solid electrolyte with the form of film that comprises the ionic conductivity inorganic substances.In this open case, by being scattered in together with binder, lithium ion conductive inorganic substances powder prepares slurries in the solvent, described slurries are directly coated on the electrode material of positive electrode or negative electrode, dry then and remove solvent so that thin film solid electrolyte to be provided.Yet, in this method, hardly may the individual processing electrolyte and need the special battery manufacturing installation to carry out electrolytical commodity production.In addition, the assembling of battery relates to the needs drying means relatively over a long time and the efficient of its reduction battery manufacturing.
Therefore, the object of the invention is to remove at above-mentioned solid electrolyte and use in the actual production of lithium rechargeable battery of described solid electrolyte because the low existing difficulty of lithium ion conducting rate, and provides and have high battery capacity and do not contain electrolytic solution, have outstanding charge-discharge cycles feature, can stablize use for a long time and be easy to the solid electrolyte making and handle in commodity production.The object of the invention is also for providing a kind of lithium rechargeable battery that uses described solid electrolyte.
In not using the solid electrolyte type cell of electrolytic solution, electrolytic solution can't impregnation in positive electrode and negative electrode, thereby can not strengthen the lithium ion conductive in positive electrode and negative electrode as in the prior art lithium ion battery that uses electrolytic solution.Therefore, another object of the present invention is and give positive electrode and negative electrode with outstanding lithium ion conducting rate and need not with electrolytic solution impregnation positive electrode and negative electrode.
Summary of the invention
As studying in great detail and result of experiment about being used for the various electrolytical of lithium rechargeable battery, inventor of the present invention has been found that (it causes the present invention), form the solid electrolyte of sheet form by the lithium ion conducting glass-ceramic powder that makes the inorganic substances powder that comprises lithium ion conducting crystal, particularly have a specific composition together with lithium ion conducting organic polymer, can in the solid electrolyte that does not contain electrolytic solution, obtain to be significantly higher than the lithium ion conducting rate of prior art polymer dielectric with ad hoc structure with specific composition.The present inventor also finds, by positive electrode and/or the negative electrode with identical inorganic substances and/or organic polymer, particularly same glass-pottery and/or organic polymer is provided, compare with prior art solid electrolyte type cell, can realize the output that improves and the charging-discharge characteristic of capacity and improvement.
In this manual, " glass-ceramic " is by amorphous solid and the prepared material of crystal, and it can make crystal be deposited on the glassy phase mutually by heat-treated glass and provide.If there is not hole substantially in intergranule or crystal grain, just degree of crystallinity is 100 quality %, and glass-ceramic comprises by the material that phase transformation provided of whole glassy phase to the crystal phase so.Pottery and agglomerated material generally can't be avoided the hole in the caused intergranule and crystal grain and the existence of crystal grain boundary in manufacture process, and in this respect, ceramic and agglomerated material can make a distinction with glass-ceramic.Particularly with regard to ionic conductivity, the ionic conductivity of pottery or agglomerated material significantly is lower than wherein contained crystal grain, and this is because have described hole and crystal grain boundary.In glass-ceramic, can prevent by the crystallization control process in the decline of the ionic conductivity of intergranule, and equal the glass-ceramic ionic conductivity of crystal grain ionic conductivity substantially thereby can be maintained.
As mentioned above, because produce without any hole that hinders ionic conduction or crystal grain boundary in intergranule and crystal grain in manufacture process, so compare with agglomerated material with general pottery, glass-ceramic has outstanding ionic conductivity.
In addition, the lithium ion conducting glass-ceramic of having found to have ad hoc structure has very high ionic conductivity and its lithium ion transference number is 1, and is highly stable solid electrolyte in atmosphere.
Find, by this glass-ceramic being provided in positive electrode and/or negative electrode or comprising the composite material of this glass-ceramic, can give positive electrode and/or negative electrode outstanding ionic conductivity enhancement function, although lithium rechargeable battery does not contain any electrolytic solution.
For reaching the object of the invention, in first aspect present invention, a kind of solid electrolyte is provided, it comprises the inorganic substances powder that contains the lithium ion conducting crystal and adds the organic polymer of inorganic or organic lithium salt and do not contain electrolytic solution, selects in the group that described organic polymer is made up of copolymer, cross-linked structure thing and its mixture of poly(ethylene oxide) and other one or more organic polymer.
In second aspect present invention, provide as at the defined solid electrolyte of first aspect, the inorganic substances that wherein constitute the inorganic substances powder that contains the lithium ion conducting crystal do not contain hole or the crystal grain boundary that hinders ionic conduction.
In this manual, " hinder the hole or the crystal grain boundary of ionic conduction " and mean the ionic conduction hindering factor, for example hole and crystal grain boundary, its will comprise the ionic conductivity of the whole inorganic substances of lithium ion conducting crystal be reduced to lithium ion conducting crystal in the inorganic substances ionic conductivity 1/10th or lower.
In third aspect present invention, provide as first or the defined solid electrolyte of second aspect, its thickness surpasses 20 μ m and high to 60 μ m.
In fourth aspect present invention, provide as first to the third aspect the defined solid electrolyte of either side, the inorganic substances powder that wherein contains the lithium ion conducting crystal has 10 -4Scm -1Or higher ionic conductivity and 9 μ m or lower mean particle diameter, and be to be contained in the solid electrolyte in the amount with 50-95 quality %.
In fifth aspect present invention, provide as the defined solid electrolyte of either side in aspect first to fourth, it has 10 -5Scm -1Or higher ionic conductivity.
In sixth aspect present invention, provide as the defined solid electrolyte of either side in aspect first to the 5th, the inorganic substances powder that wherein contains the lithium ion conducting crystal has Li 1+x+yAl xTi 2-xSi yP 3-yO 12Crystal mutually as main crystal phase, wherein x and y are 0≤x≤1 and 0≤y≤1.
In seventh aspect present invention, provide as the defined solid electrolyte of either side in aspect first to the 6th, the inorganic substances powder that wherein contains the lithium ion conducting crystal comprises the following material in mole %:
Li 2O 12-18％
Al 2O 3+Ga 2O 3 5-10％
TiO 2+GeO 2 35-45％
SiO 21-10% and
P 2O 5 30-40％。
In eighth aspect present invention, provide as the defined solid electrolyte of either side in aspect first to the 6th, the inorganic substances powder that wherein contains the lithium ion conducting crystal comprises the following material in quality %:
Li 2O 3-10％
Al 2O 3+Ga 2O 3 5-20％
TiO 2+GeO 2 25-40％
SiO 20.5-8% and
P 2O 5 40-55％。
In ninth aspect present invention, provide as first to the eight aspect the defined solid electrolyte of either side, the polymer that wherein adds inorganic or organic lithium salt has 10 -8Scm -1Ionic conductivity and be to be contained in the solid electrolyte in the amount with 5-40 quality %.
In tenth aspect present invention, a kind of solid electrolyte is provided, it comprises lithium ion conducting glass-ceramic powder and adds the organic polymer of inorganic or organic lithium salt and do not contain electrolytic solution, selects in the group that described organic polymer is made up of copolymer, cross-linked structure thing and its mixture of poly(ethylene oxide) and other one or more organic polymer.
In the present invention the tenth on the one hand, provide as defined solid electrolyte aspect the tenth, its thickness surpasses 20 μ m and high to 60 μ m.
Aspect the present invention the 12, provide as at the tenth or the tenth defined solid electrolyte on the one hand, wherein lithium ion conducting glass-ceramic powder has 10 -4Scm -1Or higher ionic conductivity and 9 μ m or lower mean particle diameter, and be to be contained in the solid electrolyte in the amount with 50-95 quality %.
Aspect the present invention the 13, provide as the defined solid electrolyte of either side in aspect the tenth to the 12, it has 10 -5Scm -1Or higher ionic conductivity.
Aspect the present invention the 14, provide as the defined solid electrolyte of either side in aspect the tenth to the 13, wherein lithium ion conducting glass-ceramic powder has Li 1+x+yAl xTi 2-xSi yP 3-yO 12Crystal mutually as main crystal phase, wherein x and y are 0≤x≤1 and 0≤y≤1.
Aspect the present invention the 15, provide as the defined solid electrolyte of either side in aspect the tenth to the 14, wherein lithium ion conducting glass-ceramic powder comprises the following material in mole %:
Li 2O 12-18％
Al 2O 3+Ga 2O 3 5-10％
TiO 2+GeO 2 35-45％
SiO 21-10% and
P 2O 5 30-40％。
Aspect the present invention the 16, provide as the defined solid electrolyte of either side in aspect the tenth to the 14, wherein lithium ion conducting glass-ceramic powder comprises the following material in quality %:
Li 2O 3-10％
Al 2O 3+Ga 2O 3 5-20％
TiO 2+GeO 2 25-40％
SiO 20.5-8% and
P 2O 5 40-55％。
Aspect the present invention the 17, provide as the defined solid electrolyte of either side in aspect the tenth to the 16, the polymer that wherein adds inorganic or organic lithium salt has 10 -8Scm -1Ionic conductivity and be to be contained in the solid electrolyte in the amount with 5-40 quality %.
In the present invention's the tenth eight aspect, a kind of lithium rechargeable battery is provided, it comprises as the defined solid electrolyte of either side in aspect the first to the 17.
Aspect the present invention the 19, provide as at the defined lithium rechargeable battery of the tenth eight aspect, it is included in the inorganic substances that contain the lithium ion conducting crystal in positive electrode and/or the negative electrode.
Aspect the present invention the 20, provide as defined lithium rechargeable battery aspect the 19, wherein the contained inorganic substances that contain the lithium ion conducting crystal do not contain hole or the crystal grain boundary that hinders ionic conduction in positive electrode and/or the negative electrode.
In the present invention the 20 on the one hand, provide as defined lithium rechargeable battery aspect the 19 or the 20, wherein the contained inorganic substances that contain the lithium ion conducting crystal are the lithium ion conducting glass-ceramic in positive electrode and/or the negative electrode.
Aspect the present invention the 22, provide as the 19 to the 20 on the one hand in the defined lithium rechargeable battery of either side, wherein in positive electrode and/or the negative electrode particle diameter of the contained inorganic substances that contain the lithium ion conducting crystal be positive electrode and/or negative electrode active material particle diameter 1/5th or lower.
Aspect the present invention the 23, provide as the defined lithium rechargeable battery of either side in aspect the 19 to the 22, wherein the contained inorganic substances that contain the lithium ion conducting crystal are that amount with the 2-35 quality % of the active material of the positive electrode that comprises inorganic substances and/or negative electrode exists in positive electrode and/or the negative electrode.
Aspect the present invention the 24, provide as the defined lithium rechargeable battery of either side in aspect the 19 to the 23, wherein the contained inorganic substances that contain the lithium ion conducting crystal comprise following material in mole % in positive electrode and/or the negative electrode:
Li 2O 12-18％
Al 2O 3+Ga 2O 3 5-10％
TiO 2+GeO 2 35-45％
SiO 21-10% and
P 2O 5 30-40％。
Aspect the present invention the 25, provide as the defined lithium rechargeable battery of either side in aspect the 19 to the 23, wherein the contained inorganic substances that contain the lithium ion conducting crystal comprise following material in quality % in positive electrode and/or the negative electrode:
Li 2O 3-10％
Al 2O 3+Ga 2O 3 5-20％
TiO 2+GeO 2 25-40％
SiO 20.5-8% and
P 2O 5 40-55％。
Aspect the present invention the 26, provide as the defined lithium rechargeable battery of either side in aspect the 19 to the 25, wherein the contained inorganic substances that contain the lithium ion conducting crystal have Li in positive electrode and/or the negative electrode 1+x+yAl xTi 2-xSi yP 3-yO 12Crystal mutually as main crystal phase, wherein x and y are 0≤x≤1 and 0≤y≤1.
Aspect the present invention the 27, provide as at the defined lithium rechargeable battery of the tenth eight aspect, it comprises glass-ceramic and the organic polymer identical with contained person in the solid electrolyte in positive electrode and negative electrode.
According to the present invention, can provide to have the high-lithium ion conductance but do not contain electrolytic solution and the solid electrolyte of individual processing easily, and the lithium rechargeable battery with high battery capacity and high output and outstanding charge-discharge cycles feature can be provided.Compare with the prior art lithium rechargeable battery, lithium rechargeable battery of the present invention does not contain electrolytic solution, and does not therefore have the dangerous of leak of liquid and burning and thereby can provide safe battery.In addition, because there is not the possibility of leak of liquid and burning, thus can improve the heat resisting temperature of battery, and therefore it can be used for hot environment and its performance that can not decay.
The inorganic substances with ad hoc structure or the glass-ceramic of the application of the invention can provide and have outstanding battery characteristics the lithium rechargeable battery of the complete solid form of (comprise and make battery can be used for the high-fire resistance matter of temperature range significantly widely).
Description of drawings
In alterations,
Fig. 1 is the schematic sectional view of the internal structure of demonstration lithium rechargeable battery of the present invention;
The figure that Fig. 2 changes for the discharge capacity of the charge-discharge cycles that shows the lithium rechargeable battery follow embodiment 3 and comparative example 3;
The figure that Fig. 3 changes for the discharge capacity of the charge-discharge cycles that shows the lithium rechargeable battery follow embodiment 4 and comparative example 4;
The figure that Fig. 4 changes for the discharge capacity of the charge-discharge cycles that shows the lithium rechargeable battery follow embodiment 5 and embodiment 6;
The figure that Fig. 5 changes for the discharge capacity of the charge-discharge cycles that shows the lithium rechargeable battery follow embodiment 7 and embodiment 8; With
The figure that Fig. 6 changes for the discharge capacity of the charge-discharge cycles that shows the lithium rechargeable battery follow embodiment 9 and embodiment 10.
Embodiment
The preferred embodiments of the invention are described now.
When comprising the inorganic substances powder that contains the lithium ion conducting crystal and the solid electrolyte of the present invention of lithium ion conducting organic polymer; or the solid electrolyte of the present invention that comprises lithium ion conducting glass-ceramic powder and lithium ion conducting organic polymer is during as battery; solid electrolyte is thin more; battery output is high more because the displacement of lithium ion is short, and battery capacity is because the electrode area of per unit volume broad can be protected and high more.Therefore, comprise the inorganic substances powder that contains the lithium ion conducting crystal and the solid electrolyte of lithium ion conducting organic polymer, or the solid electrolyte that comprises lithium ion conducting glass-ceramic powder and lithium ion conducting organic polymer should preferably have 60 μ m or lower thickness, more preferably have 50 μ m or lower thickness, and most preferably be and have 40 μ m or lower thickness.
Yet if solid electrolyte is too thin, reduction of the mechanical strength of solid electrolyte and result become difficult for individual processing solid electrolyte during its conveying and battery manufacturing so, and this is undesirable in the commodity production of battery.According to this viewpoint, therefore, solid electrolyte preferably should have and surpasses 20 μ m, 25 μ m or more and most preferably be the thickness that surpasses 30 μ m more preferably.
According to same viewpoint, solid electrolyte preferably should form with the sheet form with above-mentioned thickness.By forming the solid electrolyte of sheet form, only can help the processing of solid electrolyte, and can make solid electrolyte in advance separately and when assembled battery needs, carry and supply described solid electrolyte, can effective means make battery whereby.
In lithium rechargeable battery charging and interdischarge interval lithium ion mobility is to decide on electrolytical lithium ion conducting rate and lithium ion transference number.Therefore, the ionic conductivity that contains the inorganic substances of lithium ion conducting crystal of the present invention, or the ionic conductivity of lithium ion conducting glass-ceramic of the present invention should be preferably 1 * 10 -4Scm -1Or higher, more preferably 5 * 10 -4Scm -1Or it is higher and most preferably be 1 * 10 -3Scm -1Or it is higher.The ionic conductivity that comprises the solid electrolyte of the inorganic substances that contain the lithium ion conducting crystal or lithium ion conducting glass-ceramic should be preferably 1 * 10 -5Scm -1Or higher, more preferably 5 * 10 -5Scm -1Or it is higher and most preferably be 1 * 10 -4Scm -1Or it is higher.
As have the macroion conductance and in be contained in inorganic substances powder that contains the lithium ion conducting crystal or lithium ion conducting glass-ceramic powder in the solid electrolyte of the present invention, use inorganic substances that contain the lithium ion conducting crystal or the lithium ion conducting glass-ceramic pulverized to powder.According to the viewpoint of ionic conductivity and mechanical strength, described inorganic substances powder or the lithium ion conducting glass-ceramic powder that contains the lithium ion conducting crystal should preferably be scattered in the solid electrolyte equably.By improvement disperses and reach the thickness of being wanted of solid electrolyte, inorganic substances powder or glass-ceramic powder should preferably have 9 μ m or lower, 6 μ m or lower and most preferably be 3 μ m or lower mean particle diameter more preferably.
The lithium ion conducting glass-ceramic or in be contained in the positive electrode of lithium rechargeable battery of the present invention and/or the lithium ion conducting glass-ceramic in the negative electrode is to have Li by heat treatment 2O-Al 2O 3-TiO 2-SiO 2-P 2O 5Female glass of forming makes to carry out crystallization, and it has Li 1+x+yAl xTi 2-xSi yP 3-yO 12Crystal as its main crystal phase, wherein x and y are 0≤x≤1 and 0≤y≤1.According to the viewpoint of outstanding ionic conductivity, x and y be 0≤x≤0.4 and 0＜y≤0.6 and most preferably be 0.1≤x≤0.3 and 0.1＜y≤0.4 more preferably.
In be contained in the solid electrolyte of the present invention the inorganic substances that contain the lithium ion conducting crystal or in be contained in the positive electrode of lithium rechargeable battery of the present invention and/or the inorganic substances that contain the lithium ion conducting crystal in the negative electrode have Li 1+x+yAl xTi 2-xSi yP 3-yO 12Crystal as its main crystal phase, wherein x and y are 0≤x≤1 and 0≤y≤1.According to the viewpoint of outstanding ionic conductivity, x and y be 0≤x≤0.4 and 0＜y≤0.6 and most preferably be 0.1≤x≤0.3 and 0.1＜y≤0.4 more preferably.
Present specific description constitute the lithium ion conducting glass-ceramic or in be contained in ratio of components and its result that the composition separately of the positive electrode of lithium rechargeable battery of the present invention and/or the lithium ion conducting glass-ceramic in the negative electrode is represented with mole %.
Li 2O is for providing Li +Ionophoric indispensable composition and give glass-ceramic lithium ion conducting rate thus.For obtaining outstanding ionic conductivity, the lower limit of the amount of this composition should be preferably 12%, and more preferably 13% and most preferably be 14%.The upper limit of the amount of this composition should be preferably 18%, and more preferably 17% and most preferably be 16%.
Al 2O 3Thermal stability and the Al that is provided at the solid solution form of above-mentioned crystal in mutually for the female glass of improvement 3+Ion is effectively, and improves the lithium ion conducting rate thus.For reaching these effects, the lower limit of the amount of this composition should be preferably 5%, and more preferably 5.5% and most preferably be 6%.Yet if the amount of this composition surpasses 10%, impaired rather than modified and ionic conductivity glass-ceramic of the thermal stability of glass reduces so.Therefore, the upper limit of the amount of this composition should be preferably 10%, and more preferably 9.5% and most preferably be 9%.
TiO 2And GeO 2Help to form glass and also constitute above-mentioned crystal phase.In glass and glass-ceramic, these compositions can be through replacing each other continuously.For carrying out vitrifying, must add at least a in these compositions, and for above-mentioned crystal being precipitated mutually as main crystal mutually and improveing ionic conductivity thus, the lower limit of the total amount of these compositions should be preferably 35%, more preferably 36% and most preferably be 37%.The upper limit of the total amount of these compositions should be preferably 45%, and more preferably 43% and most preferably be 42%.
SiO 2Thermal stability and the Si that is provided at the solid solution form of above-mentioned crystal in mutually for the female glass of improvement 4+Ion is the lithium ion conducting rate that effectively and thus improves.For fully reaching these effects, the lower limit of the amount of this composition should be preferably 1%, and more preferably 2% and most preferably be 3%.Yet if the amount of this composition surpasses 10%, the ionic conductivity of glass-ceramic reduces rather than is modified so.Therefore, the upper limit of the amount of this composition should be preferably 10%, and more preferably 8% and most preferably be 7%.
P 2O 5For forming the indispensable composition of agent as glass and also being the composition that constitutes above-mentioned crystal phase.If the amount of this composition is less than 30%, when vitrifying, encounter difficulties so.Therefore, the lower limit of the amount of this composition should be preferably 30%, and more preferably 32% and most preferably be 33%.If the amount of this composition surpasses 40%, when precipitating in glass, above-mentioned crystal encounters difficulties so.Therefore, the upper limit of the amount of this composition should be preferably 40%, and more preferably 39% and most preferably be 38%.
The ratio of components of above-mentioned composition separately can be represented to obtain and the identical effect of the above-mentioned ratio of components of representing with mole % with quality % hereinafter.
About Li 2O, the lower limit of the amount of this composition should be preferably 3 quality %, 4 quality % and most preferably be 5 quality % more preferably, and the upper limit of the amount of this composition should be preferably 10 quality %, more preferably 9 quality % and most preferably be 8 quality %.
About Al 2O 3, the lower limit of the amount of this composition should be preferably 5 quality %, more preferably 6 quality % and most preferably be 7 quality %.The upper limit of the amount of this composition should be preferably 20 quality %, more preferably 19 quality % and most preferably be 18 quality %.
About TiO 2And GeO 2, the lower limit of the total amount of these compositions should be preferably 25 quality %, more preferably 26 quality % and most preferably be 27 quality %.The upper limit of the total amount of these compositions should be preferably 40 quality %, more preferably 39 quality % and most preferably be 38 quality %.
About SiO 2, the lower limit of the amount of this composition should be preferably 0.5 quality %, more preferably 1 quality % and most preferably be 2 quality %.The upper limit of the amount of this composition should be preferably 8 quality %, more preferably 7 quality % and most preferably be 6 quality %.
About P 2O 5, the lower limit of the amount of this composition should be preferably 40 quality %, more preferably 41 quality % and most preferably be 42 quality %.The upper limit of the amount of this composition should be preferably 55 quality %, more preferably 54 quality % and most preferably be 53 quality %.
With above-mentioned composition, can easily obtain glass by the casting melten glass, and have above-mentioned crystal phase and present outstanding lithium ion conducting rate by the glass-ceramic that the described glass of heat treatment obtains.
Except that above-mentioned composition, in glass-ceramic with the crystal structure that is similar to above-mentioned crystal structure, Al 2O 3Can be through Ga 2O 3Partly or all replace and TiO 2Can be through GeO 2Partly or all replace.In the manufacturing of glass-ceramic, can add a small amount of other material in the scope that does not reduce ionic conductivity, to reduce glass fusing point or improvement stability, glass.
The ionic conduction organic polymer that joins in the solid electrolyte that comprises the inorganic substances that contain the lithium ion conducting crystal or lithium ion conducting glass-ceramic should preferably form with the flexible thin sheet form when itself and inorganic substances or glass-ceramic combination, this be according to when its during as battery every volume battery capacity increase and its can form difform viewpoint because of it is flexible.
For giving the organic polymer ionic conductivity, the lithium salts of type is dissolved in the organic polymer.For this purpose, can preferably use the lithium salts that is dissolved in the organic polymer and discharges lithium ion.Described lithium salts for example comprises LiBF 4, LiCF 3SO 3, LiSO 3CH 3, LiN (SO 2CF 3) 2, LiN (SO 2C 2F 5) 2, LiC (SO 3CF 3) 3, organic ion type polysulfide, Li[B (C 6H 4O 2) 2], Li[B (C 6H 3FO 2) 2] and LiTFSI.
When the interior organic polymer that is contained in the solid electrolyte does not have ionic conductivity fully but is insulating material, even with this organic polymer and inorganic substances with macroion conductance or glass-ceramic combination, the solid electrolyte that also can't obtain having the macroion conductance.For that reason, organic polymer should have ionic conductivity.The ionic conductivity of organic polymer should be preferably 1 * 10 -8Scm -1Or higher, more preferably 1 * 10 -6Scm -1Or it is higher and most preferably be 1 * 10 -5Scm -1Or it is higher.
Be to obtain the above-mentioned ionic conductivity of organic polymer, organic polymer should be preferably a kind of in copolymer, cross-linked structure thing and its mixture of poly(ethylene oxide) and other one or more organic polymer.When only using organic polymer, if its molecular weight is diminished, ionic conductivity can increase so, but the very weak and polymer of its intensity becomes gel in this case, and the result is difficult to general fashion it be handled.On the contrary, when making its molecule quantitative change big, its intensity is improved but ionic conductivity significantly reduces.Contrast with only using organic polymer, the use of multiple polymers makes it possible to control the character that comprises ionic conductivity and intensity by type, size and the structure of the organic polymer of selecting to contain, and can realize producing the organic polymer that can be easy to handle and have outstanding ionic conductivity thus.
The macroion conductance to be given in the function that is contained in the organic polymer in the solid electrolyte in main be important to poly(ethylene oxide) carrying out.Above-mentioned other polymer is mainly carried out the function of high strength being given organic polymer.Described other polymer should be preferably for example comprised in the polymer of following material by one or more to be selected: PPOX, polyolefin, fluorine resin (for example polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride), polyamide, polyester, polyacrylate, allyl glycidyl ether and polymethacrylates.
By forming solid electrolyte by this way, can obtain than ionic conductivity high under the situation of only using poly(ethylene oxide) or other organic polymer and big processing conveniency.
If it is very little to comprise the amount of the high conduction inorganic substances powder of lithium ion conducting crystal or lithium ion conducting glass-ceramic powder in the solid electrolyte, contain so the inorganic substances of lithium ion conducting crystal or glass-ceramic the high-lithium ion conductance in solid electrolyte, can't fully present.On the contrary, if the amount of inorganic substances or glass-ceramic is excessive, the quantitative change of serving as the organic polymer of binder so gets less relatively, the result die down for sticking together of inorganic substances or glass-ceramic and organic polymer and the mobility of lithium ion in inorganic substances powder or glass-ceramic powder impaired, in addition, the intensity of solid electrolyte also dies down.For that reason, contain the inorganic substances powder of lithium ion conducting crystal or the lower limit of the amount of lithium ion conducting glass-ceramic powder in solid electrolyte of the present invention and should be preferably 50 quality %, more preferably 55 quality % and most preferably be 60 quality %.The upper limit of the amount of inorganic substances powder or glass-ceramic powder should be preferably 95 quality %, more preferably 90 quality % and most preferably be 80 quality %.
In the present invention, by adopting the ad hoc structure of above-mentioned inorganic substances or glass-ceramic and organic polymer, solid electrolyte has outstanding ionic conductivity, and keeping simultaneously is enough to make that solid electrolyte can be by the thickness of himself handling.
The positive electrode of lithium rechargeable battery of the present invention comprise at least a will be in active positive electrode material described below.Should preferably comprise positive electrode compound and positive electrode collector electrode.Negative electrode comprise at least a will be in negative electrode active material described below.Should preferably comprise positive electrode compound and positive electrode collector electrode.
The positive electrode compound of lithium rechargeable battery of the present invention and/or negative electrode compound should preferably comprise active material, ionic conduction additive and/or electronic conductive additive and with they glutinous binders together.
Positive electrode compound and/or negative electrode compound can only be made by be mixed together active material, ionic conduction additive and binder and drying composite in solvent.In this manual, this method is in hereinafter being called as simple mixed method.
Has the more viewpoint of the battery of high power capacity according to providing, preferably not by simple mixed method but make positive electrode compound and/or negative electrode compound by using so as to ionic conduction additive and/or electronic conductive additive are fixed in the lip-deep mixed method of active material particles by means of binder by the amount that reduces the ionic conduction additive.This method is in hereinafter being called as fixedly mixed method.
Because charging and the lithium ion that causes of discharge from active material remove and interpolation in active material can cause the change in volume of positive electrode compound and negative electrode compound.The expansion of active material and contraction cause electronic conductive additive and ionic conduction additive from the peeling off gradually of active material, cause lithium ion wherein to remove and add all be that the amount of impossible active material increases.This may cause the decay of charge-discharge cycles.
By utilizing fixedly mixed method, the minuteness particle of electronic conductive additive and ionic conduction additive is fixed on the surface of active material by binder, and therefore under the situation of active material expansion and contraction, can prevent the peeling off of minuteness particle of electronic conductive additive and ionic conduction additive, and therefore can add ionic conduction additive and electronic conductive additive and do not have the remarkable capacity attenuation of following charging and discharge and the capacity of per unit volume and per unit weight reduces.
Can preferably use fixedly mixed method of following method conduct, by using solvent conductive additive and binder to be mixed into the dispersing liquid of slurry condition, and described dispersing liquid is poured into or is sparged on the active material with flow at high speed or rotation, and then with mixture be higher than under the temperature of solvent boiling point dry.When mixed active material and conductive additive, the particle diameter difference of these two kinds of materials is big more, the normal more appearance interruption mixture that tends to, cause the minuteness particle that strengthens conductive additive to be deposited on tendency on each macroparticle of active material, and on the surface of active material, form the conductive additive layer thus.
Fixedly mixed method is not limited to this method.For example, particle diameter has the active material of enough big difference and conductive additive and can arise from the solvent with binder one and disperse, and then dry or by freeze drying drying in addition by hot-air.Fixedly mixed method also can realize by using conventional granulation and surface coated technology.
As the active material of the positive electrode material that is used for lithium rechargeable battery of the present invention, can use transistion metal compound.For example, can use the transistion metal compound of selecting at least a group that forms by manganese, cobalt, nickel, vanadium, niobium, molybdenum, titanium, iron and phosphorus.Because most of active material has electron conduction and ionic conductivity hardly, so should preferably use electronic conductive additive and ionic conduction additive.Described electronic conductive additive for example comprises conductive carbon, graphite, carbon fiber, metal dust, metallic fiber and electronic conductive polymer.Described ionic conduction additive for example comprises inorganic substances, ionic conducting glass-pottery and the ionic conductive polymer that contains the lithium ion conducting crystal.These electronic conductive additives and ionic conduction additive should be preferably with at 3-35 quality %, more preferably 4-30 quality % and the amount that most preferably is in the 5-25 quality % scope join in the positive electrode material (active positive electrode material).
As the active material of the negative electrode material that is used for lithium rechargeable battery of the present invention, can preferably use lithium metal, can store and discharge alloy (such as lithium-aluminium alloy and lithium-indium alloy), transistion metal compound (such as titanium and vanadium) and the carbon type material (such as graphite) of lithium.For example, can preferably use conductive carbon, graphite, carbon fiber, metal dust, metallic fiber and electronic conductive polymer as electronic conductive additive.For example, can preferably use comprise the lithium ion conducting crystal inorganic substances, ionic conducting glass-pottery and ionic conductive polymer as the ionic conduction additive.These electronic conductive additives and ionic conduction additive should be preferably with at 3-35 quality %, more preferably 4-30 quality % and the amount that most preferably is in the 5-25 quality % scope join in the negative electrode material (negative electrode active material).
When the inorganic substances that will contain the lithium ion conducting crystal or lithium ion conducting glass-ceramic joined in the positive electrode of lithium rechargeable battery and/or the negative electrode, it should be preferably powder type.
If positive electrode compound and/or negative electrode compound are to be made by simple mixed method, the mean particle diameter that contains the inorganic substances powder of lithium ion conducting crystal or lithium ion conducting glass-ceramic powder so should be preferably positive electrode and/or negative electrode active material mean particle diameter 1/5th or lower, more preferably 1/7th or lower and most preferably be 1/10th or lower.By making the mean particle diameter of inorganic substances powder or glass-ceramic powder (it is additive) compare enough little with the mean particle diameter of active material, the contact area of described additive and active material increases, and can give enough ionic conductivities by adding described additive with the amount that can not reduce battery capacity.If the mean particle diameter of inorganic substances powder or glass-ceramic powder is the same big or bigger with the mean particle diameter of positive electrode and/or negative electrode active material, must add a large amount of inorganic substances powder or glass-ceramic powder so to give positive electrode material and/or negative electrode material enough ionic conductivities.For example, if particle diameter is identical, so must addition identical with active material or than its big inorganic substances powder or glass-ceramic powder.The minimizing that this can impel the amount of active material in positive electrode material and/or the negative electrode material causes being difficult to obtain high-capacity battery.
Making by simple mixed method under the situation of positive electrode compound and/or negative electrode compound, joining positive electrode or negative electrode is essential to giving the enough ionic conductivities of positive electrode compound and/or negative electrode compound to obtain outstanding charging and discharge as the inorganic substances that contain the lithium ion conducting crystal or the lithium ion conducting glass-ceramic of ionic conduction additive, and therefore should be preferably with 10 quality % or higher, 12 quality % or higher and most preferably be 15 quality % or higher amount joins in the positive electrode and/or negative electrode active material that comprises above-mentioned inorganic substances or glass-ceramic more preferably.Yet if contain the amount increase of the inorganic substances or the lithium ion conducting glass-ceramic of lithium ion conducting crystal, the battery capacity of the amount minimizing of active material and per unit volume or per unit weight reduces in positive electrode compound and/or negative electrode compound so.Therefore, join the inorganic substances in positive electrode and/or the negative electrode or the amount of glass-ceramic and should be preferably 35 quality % or lower, more preferably 30 quality % or lower and most preferably be 25 quality % or lower.
Under situation by fixing mixed method manufacturing positive electrode compound and/or negative electrode compound, the mean particle diameter that contains the inorganic substances of lithium ion conducting crystal or lithium ion conducting glass-ceramic should be preferably positive electrode and/or negative electrode active material mean particle diameter 1/5th or lower, more preferably 1/7th or lower and most preferably be 1/10th or lower.Because can reach the enough effectiveness that is used to realize high-capacity battery less than the ionic conduction additive capacity of the amount of the situation of using simple mixed method, so the amount of ionic conduction additive should be preferably 2 quality % or higher of the active material amount that comprises inorganic substances or glass-ceramic of positive electrode and/or negative electrode, 2.5 quality % or higher and most preferably be 3 quality % or higher more preferably.For keeping active material as much as possible, contain the inorganic substances of lithium ion conducting crystal or the upper limit of lithium ion conducting glass-ceramic and should be preferably 15 quality %, more preferably 12 quality % and most preferably be 10 quality %.The situation of electronic conductive additive is identical, and littler by the particle diameter that makes electronic conductive additive, can be with the identical or better effect that reaches electronic conductive additive than previous amount still less.
The inorganic substances that contain the lithium ion conducting crystal that join positive electrode and negative electrode and ionic conductive polymer or ionic conducting glass-pottery and organic polymer should be preferably with in be contained in inorganic substances or glass-ceramic inorganic substances or glass-ceramic and the organic polymer identical in the solid electrolyte with organic polymer.In this case, identical inorganic substances that contain the lithium ion conducting crystal or glass-ceramic mean inorganic substances that contain the lithium ion conducting crystal or the glass-ceramic with phase allomeric phase.Because crystal is identical mutually, so in the interior polymer that is contained in the electrolyte and in the ion mobile mechanism that is contained in the polymer in the electrode material be unified, and make ion between electrolyte and the electrode move smoothly and carry out, therefore can provide to have the higher output and the battery of high power capacity more.
As by mixing and binding active material and conductive additive and make used binder under the situation of positive electrode compound and/or negative electrode compound, can use PVdF, PTFE and SBR rubber, but preferably use the ionic conduction binder, because it can give ionic conductivity.
The ionic conduction binder comprises polymeric material, for example poly(ethylene oxide), PPOX, polyolefin, fluorine resin (for example polytetrafluoroethylene, polychlorotrifluoroethylene and polyvinylidene fluoride), polyamide, polyester, polyacrylate and its copolymer, cross-linked structure thing and mixture.Also may be by adding the lithium salts of wanting (LiBF for example 4, LiSO 3CF 3, LiSO 3CH 3, LiN (SO 2CF 3) 2, LiN (SO 2C 2F 5) 2, LiC (SO 2CF 3) 3With organic ion type polysulfide) increase the ionic conductivity of these materials.
Embodiment
To and utilize the specific embodiment of the lithium rechargeable battery of prepared this solid electrolyte to be described about the solid electrolyte, the solid electrolyte that comprises lithium ion conducting glass-ceramic and lithium ion conducting organic polymer that comprise the inorganic substances that contain the lithium ion conducting crystal and lithium ion conducting organic polymer now according to the present invention.Also carry out about the description of comparative example to explain the advantage of the embodiment of the invention.Yet, the invention is not restricted to these embodiment and can in spirit of the present invention and category, make amendment.
Embodiment 1
The preparation of lithium ion conducting glass-ceramic:
H weighs 3PO 4, Al (PO 3) 3, Li 2CO 3, SiO 2And TiO 2Raw material also evenly mix to make 35.0%P 2O 5, 7.5%Al 2O 3, 15.0%Li 2O, 38.0%TiO 2And 4.5%SiO 2The composition of (being expressed as mole %) in oxide.Mixture is placed the platinum jar and under 1500 ℃, stirred melten glass in three hours simultaneously in electric furnace heating and fusion.Then, fused mass is splashed in the flowing water to produce sheet glass.In 950 ℃ of following heating glass 12 hours with crystallization and obtain target glass-pottery thus.By powder x-ray diffraction, confirm that the main crystal that is precipitated is Li mutually 1+x+yAl xTi 2-xSi yP 3-yO 12(0≤x≤0.4,0＜y≤0.6).Pulverize the glass-ceramic sheet that is produced and obtain having 2 μ m mean particle diameters and the glass-ceramic minuteness particle of the maximum particle diameter of 8 μ m with ball mill.
The preparation of solid electrolyte:
With glass-ceramic that obtains thus and the LiBF that adds as lithium salts 4The copolymer of poly(ethylene oxide) and PPOX evenly mix in alcohol solvent with 80: 20 ratio, and mixture coated on the PET film of using lift-off processing, and under room temperature dry and then further in 120 ℃ of following drying under reduced pressure to remove solvent by evaporation.Another PET film of using lift-off processing is attached on the solid electrolyte that obtains thus.Then push to remove the bubble of staying in the composite electrolyte (solid electrolyte just) in 150 ℃ of following heating composite electrolytes and with roll press.Then, divest film at the PET of solid electrolyte both sides.Resulting solid electrolyte flake tool 40 μ m thickness.By with the described solid electrolyte of a pair of corrosion resistant plate fixing and use these corrosion resistant plates to prepare the sample that is used to measure the lithium ion conducting rate as electrode.The impedance of measuring samples under 25 ℃ of room temperatures is to calculate ionic conductivity.Found that ionic conductivity is 1.3 * 10 -4Scm -1
Comparative example 1
Mix the glass-ceramic powder identical and do not add the poly(ethylene oxide) of any lithium salts and the copolymer of PPOX, and form solid electrolyte flake to measure the ionic conductivity of described thin slice in the mode identical with embodiment 1 with embodiment 1.The ionic conductivity of the described thin slice of result is 7 * 10 -9Scm -1, its ionic conductivity that is lower than embodiment 1 surpasses four figures.
Embodiment 2
The preparation of positive electrode:
Use commercially available LiCoO 2(mean particle diameter 6 μ m) are as the active material of positive electrode.With this active positive electrode material with add the acetylene black electronic conductive additive and as the lithium salts LiBF of ionic conduction additive 4Poly(ethylene oxide) mix in alcohol solvent with the copolymer and the binder of PPOX.Evenly coat the gained mixture on the aluminium sheet that constitutes the positive electrode collector electrode and dry positive electrodes under 120 ℃ with the generation sheet form with 16 μ m thickness.Described positive electrode has 100 μ m thickness.
The preparation of negative electrode:
Use commercially available powdered graphite (mean particle diameter 10 μ m) as negative electrode.With this negative electrode material and the lithium salts LiBF that adds as the ionic conduction additive 4Poly(ethylene oxide) mix in alcohol solvent with the copolymer and the binder of PPOX.The gained mixture is coated on the copper coin with 12 μ m thickness that constitutes the negative electrode collector electrode, and dry down in 120 ℃ to produce the negative electrode of sheet form.Described negative electrode has 70 μ m thickness.
The battery assembling:
Positive electrode, the solid electrolyte and the negative electrode that form with sheet form that make in embodiment 1 is stacked in turn, in 150 ℃ of heating down, with the roll press extruding and be cut into 25 * 40mm thin slice.Battery unit thickness is 230 μ m.Then in decompression dry cell unit and being sealed in the laminated sheet that lead-in wire connects down with assembled battery.The internal structure of this battery is shown in Fig. 1 part.Among Fig. 1, reference character 1 expression positive electrode collector electrode, 2 expression positive electrode compounds, 3 expression composite electrolytes (solid electrolyte), 4 expression negative electrode compounds and 5 expression negative electrode collector electrodes.
Under the condition of 25 ℃ of room temperatures, 0.3mA constant current, 4.2V charging cut-ff voltage and 3.0V discharge cut-off voltage to charging through assembled battery-discharge measuring.Initial discharge capacity be 19.4mAh and after repeating 20 circulations discharge capacity be 19.0mAh, it is 98% of an initial discharge capacity.
Comparative example 2
Thin slice by using comparative example 1 is assembled the battery identical with embodiment 2 as electrolyte sheet, and charges-discharge measuring under the condition identical with embodiment 2.Only energy measurement is to 1mAh or lower.
Embodiment 3
The preparation of solid electrolyte:
The copolymer of resulting glass-ceramic powder among the embodiment 1 and the poly(ethylene oxide), PPOX and the 2-methoxyethoxyethyl glycidol ether that add LiTFSI (the bis trifluoromethyl sulfimide lithium) ratio with 75: 25 is evenly mixed in the ethyl-methyl ketone solvent.Then coat mixture on the PET film of using lift-off processing and under room temperature dry and then further in 130 ℃ of following drying under reduced pressure to remove solvent by evaporation.Another PET film of using lift-off processing is attached on the solid electrolyte that obtains thus.Then push to remove the bubble of staying in the composite electrolyte in 130 ℃ of following heating composite electrolytes and with roll press.Then divest film at the PET of solid electrolyte both sides.Resulting solid electrolyte has 35 μ m thickness.
The preparation of positive electrode:
Use commercially available LiMn 2O 3(mean particle diameter 10 μ m) are as the active material of positive electrode.With this active material with add the acetylene black electronic conductive additive and in the ethyl-methyl ketone solvent, mix as the copolymer and the binder of poly(ethylene oxide), PPOX and the 2-methoxyethoxyethyl glycidol ether of the lithium salts LiTFSI (bis trifluoromethyl sulfimide lithium) of ionic conduction additive.Then the gained mixture is evenly coated on the aluminium sheet with 16 μ m thickness that constitutes the positive electrode collector electrode, and dry down in 130 ℃ to produce the positive electrode of sheet form.Described positive electrode has 100 μ m thickness.
The preparation of negative electrode:
Use commercially available Li 4Ti 5O 12(mean particle diameter 3 μ m) are as negative electrode active material.Copolymer and the binder of this active material with the poly(ethylene oxide), PPOX and the 2-methoxyethoxyethyl glycidol ether that add the lithium salts LiTFSI (bis trifluoromethyl sulfimide lithium) that is used as the ionic conduction additive mixed in the ethyl-methyl ketone solvent.Then the gained mixture is coated on the copper coin with 12 μ m thickness that constitutes the negative electrode collector electrode, and dry down in 130 ℃ to produce the negative electrode of sheet form.Described negative electrode has 70 μ m thickness.
The battery assembling:
Positive electrode, the solid electrolyte and the negative electrode that form with sheet form that make in embodiment 1 is stacked in turn, in 150 ℃ of heating down, with the roll press extruding and be cut into 25 * 40mm thin slice.Battery unit thickness is 235 μ m.Then in decompression dry cell unit and being sealed in the laminated sheet that lead-in wire connects down with assembled battery.
Under the condition of 25 ℃ of room temperatures, 0.2mA constant current, 3.0V charging cut-ff voltage and 1.5V discharge cut-off voltage to charging through assembled battery-discharge measuring.Initial discharge capacity be 14.7mAh and after repeating 20 circulations discharge capacity be 14.6mAh, it is approximately identical with initial discharge capacity.
Comparative example 3
By using the copolymer electrolyte sheet of the poly(ethylene oxide), PPOX and the 2-methoxyethoxyethyl glycidol ether that add LiTFSI, it does not contain glass-ceramic.By using positive electrode identical and negative electrode assembled battery and under the condition identical, charging-discharge measuring with embodiment 3 with embodiment 3.Initial discharge capacity is 13.3mAh, and it is the capacity a shade below embodiment 3.This is because electrolyte sheet does not contain glass-ceramic with macroion conductance and the impedance of therefore moving for ion is very high.In addition, in comparative example 3, between positive electrode and the negative electrode internal short-circuit takes place through being everlasting, and thereby the test of nearly 20 circulations can't carry out.This is because positive electrode is taken place because of the roll press extruding partly contacts or almost contacts each other with negative electrode when assembled battery.Because this internal short-circuit can not take place, so be contained in the good sept function of glass-ceramic powder tool in the electrolyte sheet of embodiment 3 in confirming in the battery of embodiment 3.
Following the discharge capacity of charge-discharge cycles of the lithium rechargeable battery of embodiment 3 and comparative example 3 to change is shown among Fig. 2.
Embodiment 4
The preparation of solid electrolyte:
Pulverize in embodiment 1 resulting glass-ceramic so that the glass-ceramic attritive powder with 0.3 μ m mean particle diameter and the maximum particle diameter of 3 μ m to be provided by using wet ball mill.With described glass-ceramic powder and interpolation LiCF 3SO 3The copolymer of poly(ethylene oxide) and PPOX evenly mix in THF (oxolane) solvent with 65: 35 ratio.Mixture coated peels off on the pretreated PET film, under room temperature dry and then further in 110 ℃ of following drying under reduced pressure to remove solvent by evaporation.Attach on the solid electrolyte that obtains thus peeling off pretreated another PET film.Then push to remove the bubble of staying in the composite electrolyte (solid electrolyte just) in 130 ℃ of following heating composite electrolytes and with roll press.Resulting solid electrolyte flake has 32 μ m thickness.
The preparation of positive electrode:
Use commercially available LiCoO 2(mean particle diameter 6 μ m) are as the active material of positive electrode.With described active positive electrode material with add the acetylene black electronic conductive additive and as the lithium salts LiCF of ionic conduction additive 3SO 3Poly(ethylene oxide) mix in the THF solvent with the copolymer and the binder of PPOX.The gained mixture is evenly coated on the aluminium sheet with 12 μ m thickness that constitutes the positive electrode collector electrode, and dry down in 120 ℃ to produce the positive electrode of sheet form.Described positive electrode has 40 μ m thickness.
The preparation of negative electrode:
Use commercially available powdered graphite (mean particle diameter 3 μ m) as negative electrode.With this negative electrode material and the lithium salts LiCF that adds as the ionic conduction additive 3SO 3Poly(ethylene oxide) mix in the THF solvent with the copolymer and the binder of PPOX.The gained mixture is coated on the copper coin with 10 μ m thickness that constitutes the negative electrode collector electrode, and dry down in 120 ℃ to produce the negative electrode of sheet form.Described negative electrode has 30 μ m thickness.
The battery assembling:
A side that is the solid electrolyte that makes among the embodiment 1 divests to be peeled off after the pretreated PET film, positive electrode material is attached to this side of solid electrolyte by means of roll press.Then, the solid electrolyte opposite side divest peel off pretreated PET film after, negative electrode material is attached to this side of solid electrolyte by means of roll press.Then heat composite solid electrolyte down and push and be cut into 25 * 40mm thin slice with roll press in 150 ℃.Battery unit thickness is about 116 μ m.Then in decompression dry cell unit and being sealed in the laminated sheet that lead-in wire connects down with assembled battery.
Under the condition of 25 ℃ of room temperatures, 0.2mA constant current, 4.2V charging cut-ff voltage and 3.2V discharge cut-off voltage to charging through assembled battery-discharge measuring.Initial discharge capacity be 11.3mAh and after repeating 20 circulations discharge capacity be 10.9mAh, its be initial discharge capacity about 96% or more.
Comparative example 4
The SiO 2 powder that has 0.3 μ m mean particle diameter by use replaces the lithium ion conducting glass-ceramic, prepares composite electrolyte (solid electrolyte) with the method identical with embodiment 4.Use positive electrode identical and negative electrode assembled battery and under the condition identical, charge-discharge measuring with embodiment 4 with embodiment 4.Initial discharge capacity be 8.3mAh and after repeating 20 circulations discharge capacity be 7.1mAh.Compare with embodiment 4, the decay after repetitive cycling is big and capacity is littler far away.Following the discharge capacity of charge-discharge cycles of the lithium rechargeable battery of embodiment 4 and comparative example 4 to change is shown among Fig. 3.The battery capacity of embodiment 4 is higher because it contains the glass-ceramic that has the macroion conductance in a large number, and thereby electrolytical conductance also help ion to move thus far above the electrolyte that only contains polymer.By contrast, the battery of comparative example 4 presents some conductances improvement by adding silicon dioxide, but this improved effect to compare with the battery of embodiment 4 be quite little.
Comparative example 5
The preparation of solid electrolyte:
With glass-ceramic powder and the LiBF that adds as lithium salts 4Poly(ethylene oxide) in acetone solvent, evenly mix.The gained mixture is coated on the moulding plate with 50 μ m thickness, dry and with the roll press extruding for having the solid electrolyte flake of 30 μ m thickness.
The preparation of positive electrode:
Use LiMn 2O 4As active positive electrode material.With described active positive electrode material with as the acetylene black of electronic conductive additive, as the ionic conduction additive and contain Li 1+x+yAl xTi 2-xSi yP 3-yO 12Glass-ceramic powder and binder as main crystal phase mix in acetone solvent.The gained mixture coated on the aluminium sheet that constitutes the positive electrode collector electrode until about 50 μ m thickness to produce positive electrode layer with 10 μ m thickness.
The preparation of negative electrode:
Use Li 4Ti 5O 12As negative electrode active material.With described negative electrode active material with mix in acetone solvent as the glass-ceramic powder of ionic conduction additive with as the PVdF of binder.The gained mixture coated on the copper coin that constitutes the negative electrode collector electrode until about 50 μ m thickness to produce positive electrode layer with 10 μ m thickness.
The battery assembling:
Positive electrode layer and positive electrode layer are attached to solid electrolyte (spacer) both sides of sheet form, and with roll press with the battery of composite bed extruding for sheet form with 150 μ m thickness.Thin slice is cut into 25 * 40mm thin slice and lead-in wire is connected in positive electrode collector electrode and negative electrode collector electrode.Under the condition identical, carry out the charge-discharge cycles test with embodiment 4.Initial discharge capacity and the discharge capacity after repeating 20 circulations are shown in Table 1.
Table 1
Embodiment 4
Capacity (mAh) 10.9 after 11.3 20 circulations of initial capacity (mAh)
Comparative example 5
Capacity (mAh) 7.9 after 8.5 20 circulations of initial capacity (mAh)
Compare with the comparative example 5 of the conventional binder that uses electrode material, embodiment 4 presents higher capacity.This be because, in embodiment 4, in solid electrolyte, except that poly(ethylene oxide), also use other organic polymer and realize that thus the macroion conductance keeps the processing convenience simultaneously, in addition, be used for electrolyte and electrode material by ionic conductive polymer, not only realize high conductivity but also make ion interface between electrolyte and the electrode move becoming smooth same type.
Embodiment 5
The preparation of lithium ion conducting glass-ceramic:
H weighs 3PO 4, Al (PO 3) 3, Li 2CO 3, SiO 2And TiO 2Raw material also evenly mix to make 35.0%P 2O 5, 7.5%Al 2O 3, 15.0%Li 2O, 38.0%TiO 2And 4.5%SiO 2The composition of (being expressed as mole %) in oxide.Mixture is placed the platinum jar and under 1500 ℃, stirred melten glass in three hours simultaneously in electric furnace heating and fusion.Then fused mass is splashed in the flowing water to produce sheet glass.In 950 ℃ of following heating glass 12 hours with crystallization and obtain target glass-pottery thus.By powder x-ray diffraction, confirm that the main crystal that is precipitated is Li mutually 1+x+yAl xTi 2-xSi yP 3-yO 12(0≤x≤0.4,0＜y≤0.6).Pulverize the glass-ceramic sheet that is produced and obtain having 2 μ m mean particle diameters and the glass-ceramic attritive powder of the maximum particle diameter of 9 μ m with ball mill.Further pulverize described attritive powder A and obtain containing the slurries B of glass-ceramic attritive powder with the maximum particle diameter of 0.2 μ m mean particle diameter and 0.3 μ m with wet ball mill.
The preparation of solid electrolyte:
With glass-ceramic powders A that obtains thus and the LiBF that adds as lithium salts 4The copolymer of poly(ethylene oxide) and PPOX evenly mix in alcohol solvent with 80: 20 ratio, and with mixture coat peel off on the pretreated PET film and under room temperature dry and then further in 120 ℃ of following drying under reduced pressure to remove solvent by evaporation.Attach on the solid electrolyte that obtains thus peeling off pretreated another PET film.Then push to remove the bubble of staying in the composite electrolyte (solid electrolyte just) in 150 ℃ of following heating composite electrolytes and with roll press.Then divest film at the PET of solid electrolyte both sides.Resulting solid electrolyte flake has 30 μ m thickness.By with the described solid electrolyte of a pair of corrosion resistant plate fixing and use these corrosion resistant plates to prepare the sample that is used to measure the lithium ion conducting rate as electrode.The impedance of measuring samples under 25 ℃ of room temperatures is to calculate ionic conductivity.Found that ionic conductivity is 1.6 * 10 -4Scm -1
The preparation of positive electrode:
Use commercially available LiCoO 2(mean particle diameter 6 μ m) are as the active material of positive electrode.With electronic conductive additive acetylene black (mean particle diameter 50 μ ms) and the interpolation LiBF of twin shaft blender with described active positive electrode material and 5 quality % (based on active positive electrode material) 4The poly(ethylene oxide) of (as the lithium salts of ionic conduction additive) is mixed in alcohol solvent with the copolymer and the binder of PPOX.The gained mixture is evenly coated on the aluminium sheet with 16 μ m thickness that constitutes the positive electrode collector electrode, and dry down in 120 ℃ to produce the positive electrode of sheet form.Described positive electrode has 50 μ m thickness.
The preparation of negative electrode:
Use commercially available powdered graphite (mean particle diameter 10 μ m) as negative electrode.With double shaft kneader with this negative electrode material with add LiBF 4Poly(ethylene oxide) mix in alcohol solvent with the copolymer of PPOX.Coat the gained mixture on the copper coin that constitutes the negative electrode collector electrode and dry negative electrodes under 120 ℃ with the generation sheet form with 12 μ m thickness.Described negative electrode has 40 μ m thickness.
The battery assembling:
Positive electrode, solid electrolyte and negative electrode is stacked in turn, in 150 ℃ of heating down, push and be cut into 25 * 40mm thin slice with roll press.Battery unit thickness is 130 μ m.Then in decompression dry cell unit and being sealed in the laminated sheet that lead-in wire connects down with assembled battery.The internal structure of described battery is shown in Fig. 1.
In 25 ℃ of room temperatures, 0.2mA/cm 2Under the condition of constant current, 4.2V charging cut-ff voltage and 3.0V discharge cut-off voltage to charging through assembled battery-discharge measuring.Initial discharge capacity be 12.2mAh and after repeating 20 circulations discharge capacity be 11.3mAh, it is 92% of an initial discharge capacity.
Embodiment 6
To join respectively in positive electrode and the negative electrode in the glass-ceramic attritive powder slurries B of the amount of solid 20 quality %, and in others with the mode assembled battery identical with embodiment 5.Charge-discharge measuring in the mode identical with embodiment 5.Initial discharge capacity be 13.8mAh and after repeating 20 circulations discharge capacity be 13.2mAh, it is 96% of an initial discharge capacity.
Following the discharge capacity of charge-discharge cycles of the lithium ion conducting battery of embodiment 5 and embodiment 6 to change is shown among Fig. 4.
In the battery of embodiment 5 and embodiment 6, initial discharge capacity is very big and follow the capacity attenuation of charge-discharge cycles relatively little.Use the outstanding especially result of embodiment 6 tools of lithium ion conducting glass-ceramic.
Embodiment 7
The preparation of solid electrolyte:
Prepared glass-ceramic powders A among the embodiment 5 is evenly mixed in alcohol solvent with adding as the copolymer of the poly(ethylene oxide) of the LiTFSI of lithium salts and the PPOX ratio with 75: 25.Mixture coated peels off on the pretreated PET film, and under room temperature dry and then further in 120 ℃ of following drying under reduced pressure to remove solvent by evaporation.Attach on the solid electrolyte that obtains thus peeling off pretreated another PET film.Then under 130 ℃, heat composite electrolyte, and push to remove the bubble of staying in the solid electrolyte with roll press.Divest film at the PET of electrolyte both sides.The solid electrolyte that obtains thus has 26 μ m thickness.
The preparation of positive electrode:
For producing the positive electrode compound, use commercially available streaming comminutor.By in alcohol solvent, mixing the Ketjen black as electronic conductive additive (ketjenblack) (mean particle diameter 40nm), preparing spray suspension liquid as the glass-ceramic attritive powder slurries B of ionic conduction additive with as the poly(ethylene oxide) of the interpolation LiTFSI of binder and the copolymer of PPOX in solid 5 quality % (based on active positive electrode material) in solid 5 quality % (based on active positive electrode material).
Use commercially available LiMn 2O 4(mean particle diameter 10 μ m) are as the active material of positive electrode.The spray suspension liquid that places the streaming comminutor also will prepare in the above described manner described active positive electrode material sparges on the active positive electrode material of 90 ℃ of current downflow, causes the etoh solvent evaporation thus and causes that electronic conductive additive and ionic conduction additive are fixed in the particle surface of active material.By the positive electrode compound dispersion a little once more of using ethanol that its surface is covered through conductive additive, and evenly coat on the aluminium sheet that constitutes the positive electrode collector electrode with 20 μ m thickness.Dry positive electrode material is to produce positive electrode under 120 ℃.The positive electrode compound has 65 μ m thickness.
The preparation of negative electrode:
For producing the negative electrode compound, be used to produce the commercially available streaming comminutor of positive electrode compound.
By in alcohol solvent, mixing the Ketjen black as electronic conductive additive (mean particle diameter 40nm), preparing spray suspension liquid as the glass-ceramic attritive powder slurries B of ionic conduction additive with as the poly(ethylene oxide) of the interpolation LiTFSI of binder and the copolymer of PPOX in solid 5 quality % (based on negative electrode active material) in solid 5 quality % (based on negative electrode active material).
Will be as the commercially available Li of negative electrode active material 4Ti 5O 12Granulate to having the particle of 3 μ m mean particle diameters.Described negative electrode active material is placed the streaming comminutor; and the spray suspension liquid that will prepare in the above described manner sparges on the negative electrode active material of 90 ℃ of current downflow, causes the etoh solvent evaporation thus and causes that electronic conductive additive and ionic conduction additive are fixed in the particle surface of active material.By the negative electrode compound dispersion a little once more of using ethanol that its surface is covered through conductive additive, and evenly coat on the copper coin that constitutes the negative electrode collector electrode with 18 μ m thickness.Dry negative electrode material is to produce negative electrode under 120 ℃.The negative electrode compound has 50 μ m thickness.
The battery assembling:
Positive electrode, solid electrolyte and negative electrode is stacked in turn, in 150 ℃ of heating down, push and be cut into 25 * 40mm thin slice with roll press.Battery unit thickness is 175 μ m.Then in decompression dry cell unit and being sealed in the laminated sheet that lead-in wire connects down with assembled battery.
In 25 ℃ of room temperatures, 0.2mA/cm 2Under the condition of constant current, 3.5V charging cut-ff voltage and 2.0V discharge cut-off voltage to charging through assembled battery-discharge measuring.Initial discharge capacity be 18.9mAh and after repeating 20 circulations discharge capacity be 18.0mAh, it is 95% of an initial discharge capacity.
Embodiment 8
With prepared glass-ceramic attritive powder A with 2 μ m mean particle diameters among the embodiment 5 with the amount of 10 quality % ionic conduction additive, and with the mode assembled battery identical with embodiment 7 as positive electrode and negative electrode.
In 25 ℃ of room temperatures, 0.2mA/cm 2Under the condition of constant current, 3.5V charging cut-ff voltage and 2.0V discharge cut-off voltage to charging through assembled battery-discharge measuring.Initial discharge capacity be 13.7mAh and after repeating 20 circulations discharge capacity be 9.6mAh, it is 70% of an initial discharge capacity.
Following the discharge capacity of charge-discharge cycles of the lithium ion conducting battery of embodiment 7 and embodiment 8 to change is shown among Fig. 5.
In the battery of embodiment 7 and embodiment 8, initial discharge capacity is very big and follow the capacity attenuation of charge-discharge cycles relatively little.The embodiment 7 that use has the lithium ion conducting glass-ceramic of especially little mean particle diameter has outstanding especially result.
Embodiment 9
For producing the positive electrode compound, use commercially available spray dryer.Will be as the LiNi of active positive electrode material 0.8Co 0.2O 2The carbon nano-fiber as electronic conductive additive (mean particle diameter 80nm) of (mean particle diameter 3 μ m), 2 quality % (based on active positive electrode material), the SiO of 4 quality % (based on active positive electrode material) as the ionic conduction additive 2Attritive powder (mean particle diameter 50nm) and in methyl alcohol and ethanol mixed solvent, be mixed together with supending as the poly(ethylene oxide) of the interpolation LiTFSI of binder and the copolymer of PPOX.Spray described suspension and when stirring, use the spray dryer drying, and make electronic conductive additive and ionic conduction additive be fixed in the particle surface of active material by evaporating solvent.By the use alcohol solvent the described positive electrode compound that covers through conductive additive is disperseed a little, and evenly coat on the aluminium sheet that constitutes the positive electrode collector electrode with 20 μ m thickness.Follow in 120 ℃ of following dry composite materials to produce positive electrode.The positive electrode compound has 45 μ m thickness.
The preparation of negative electrode:
Be to produce the negative electrode compound, use and be used to prepare the identical spray dryer of positive electrode compound.Will be as the commercially available Li of negative electrode active material 4Ti 5O 12(through granulating), the carbon nano-fiber as electronic conductive additive (mean particle diameter 80nm) of 2 quality % (based on negative electrode active material), the SiO of 3 quality % (based on negative electrode active material) as the ionic conduction additive to having the particle of 3 μ m mean particle diameters 2Attritive powder (mean particle diameter 50nm) and in methyl alcohol and ethanol mixed solvent, be mixed together with supending as the poly(ethylene oxide) of the interpolation LiTFSI of binder and the copolymer of PPOX.Spray described suspension and when stirring, use the spray dryer drying, and make electronic conductive additive and ionic conduction additive be fixed in the particle surface of active material by evaporating solvent.By the use alcohol solvent the described negative electrode compound that covers through conductive additive is disperseed a little, and evenly coat on the copper coin that constitutes the negative electrode collector electrode with 20 μ m thickness.Follow in 120 ℃ of following dry composite materials to produce negative electrode.The negative electrode compound has 45 μ m thickness.
The battery assembling:
With positive electrode, prepared solid electrolyte and negative electrode are stacked in turn in embodiment 7, in 150 ℃ of heating down, with the roll press extruding and be cut into 25 * 40mm thin slice.Battery unit thickness is 175 μ m.Then in decompression dry cell unit and being sealed in the laminated sheet that lead-in wire connects down with assembled battery.
In 25 ℃ of room temperatures, 0.2mA/cm 2Under the condition of constant current, 3.5V charging cut-ff voltage and 2.0V discharge cut-off voltage to charging through assembled battery-discharge measuring.Initial discharge capacity be 15.5mAh and after repeating 20 circulations discharge capacity be 12.4mAh, it is 80% of an initial discharge capacity.
Embodiment 10
Make battery in the mode identical with embodiment 9, prepared glass-ceramic attritive powder slurries B is alternative in employed SiO among the embodiment 9 among the embodiment 5 except being used in 2Attritive powder is as the ionic conduction additive of positive electrode and negative electrode, and its amount is in 4 quality % of solid active positive electrode material with in 3 quality % of solid negative electrode active material.Under the condition identical, charge-discharge measuring with embodiment 8.Initial discharge capacity be 18.6mAh and after repeating 20 circulations discharge capacity be 17.7mAh, it is 95% of an initial discharge capacity.
Following the discharge capacity of charge-discharge cycles of the lithium ion conducting battery of embodiment 9 and embodiment 10 to change is shown among Fig. 6.
In the battery of embodiment 9 and embodiment 10, initial discharge capacity is very big and follow the capacity attenuation of charge-discharge cycles relatively little.Use the embodiment 10 of lithium ion conducting glass-ceramic to have outstanding especially result.
Comparative example 6
Make battery in the mode identical with embodiment 9, except using LiI to be contained in glass-ceramic powders A in the solid electrolyte of embodiment 9 in substituting with same amount, described LiI is a lithium ion conducting glass-ceramic and through pulverizing to having the particle of 2 μ m mean particle diameters.Under the condition identical, charge-discharge measuring with embodiment 9.Initial discharge capacity be 10.2mAh and after repeating 20 circulations discharge capacity be 6.1mAh, it only is about 60% of an initial discharge capacity.
As mentioned before, the lithium rechargeable battery of the present invention that comprises the solid electrolyte that contains the lithium ion conducting glass-ceramic has high output and outstanding charging-discharge characteristic.In addition,, lithium rechargeable battery of the present invention do not separate solution, so can obtain battery as safe as a house because not containing electromechanics.
According to the present invention, the polymer that is endowed lithium ion conductive by use is as the binder that is used for solid electrolyte and adopt the ad hoc structure of polymer, can realize having the lithium rechargeable battery of high power and outstanding charging-discharge characteristic.
In addition, the lithium rechargeable battery of the present invention that comprises the lithium ion conducting glass-ceramic in electrode has realized having the battery of high power and outstanding charging-discharge characteristic, though it is not for containing the complete solid state battery that electromechanics is separated solution.
Industrial usability
Therefore the electrolyte of the present invention that includes organic polymer and lithium ion conducting glass-ceramic has high-lithium ion conductance and highly stable on electrochemistry, and it not only can be used for lithium rechargeable battery and also can be used for lithium primary cell, is called as electrochemical capacitor, DSSC and the use lithium ion of mixed capacitor other electrochemical assembly as the electric charge transfer vector.Some examples of these electrochemical assemblies will be in hereinafter describing.
By want sensitive electrode is connected to electrolyte, electrolyte can be used for all gases transducer and other detector.For example, by using carbonate as electrode, it can be used as the carbon dioxide gas bulk detector.By using nitrate as electrode, it can be used as NO xDetector.By using sulfate as electrode, it can be used as SO xDetector.By assembling electrolyte in electrolytic cell, it can be used as and decomposes and catch NO in the waste gas xAnd SO xElectrolyte.
By will be owing to inserting or removing lithium ion and the inorganic or organic compound of painted or variable color is attached on the electrolyte or by sticking thereon such as the transparency electrode of ITO, can form electric chromium component, the Electrochromic Display of the little power consumption with memory capacity can be provided whereby.
Because the electrolytical ionic conduction of the present invention path has the optimum size that allows lithium ion pass through, it optionally allows lithium ion pass through when the basic ion except that lithium ion also exists.Therefore, electrolyte can be used as the dividing plate of lithium ion selective collection device or the dividing plate of lithium ion-selective electrode.Because hour lithium ion is higher by speed when mass of ion, so electrolyte can be used for the isotope of separating Li ion.This makes it possible to concentrate and separate 6Li concentrate (occurring in nature exists with 7.42% ratio), and it is essential by the protective material that is used to produce as the tritium of thermonuclear reactor fuel.
Because in the lithium ion conducting glass-ceramic powder that is contained in electrolyte and the electrode have high-lithium ion conductance and highly stable on electrochemistry, so can be by hybrid glass-ceramic powders in other resin or coating material used as the additive that is used to give ionic conductivity, antistatic purpose and control surface electromotive force etc.

Claims (27)

1. solid electrolyte, it comprises the inorganic substances powder that contains the lithium ion conducting crystal and adds the organic polymer of inorganic or organic lithium salt and do not contain electrolytic solution, selects in the group that described organic polymer is made up of copolymer, cross-linked structure thing and its mixture of poly(ethylene oxide) and other one or more organic polymer.
2. solid electrolyte according to claim 1, the described inorganic substances that contain the inorganic substances powder of lithium ion conducting crystal of wherein said formation do not contain hole or the crystal grain boundary that hinders ionic conduction.
3. solid electrolyte according to claim 1 and 2, its thickness surpass 20 μ m and high to 60 μ m.
4. according to each described solid electrolyte of claim 1 to 3, the wherein said inorganic substances powder that contains the lithium ion conducting crystal has 10 -4Scm -1Or higher ionic conductivity and 9 μ m or lower mean particle diameter, and be to be contained in the described solid electrolyte in the amount with 50-95 quality %.
5. according to each described solid electrolyte of claim 1 to 4, it has 10 -5Scm -1Or higher ionic conductivity.
6. according to each described solid electrolyte of claim 1 to 5, the wherein said inorganic substances powder that contains the lithium ion conducting crystal has Li 1+x+yAl xTi 2-xSi yP 3-yO 12Crystal mutually as main crystal phase, wherein x and y are 0≤x≤1 and 0≤y≤1.
7. according to each described solid electrolyte of claim 1 to 6, the wherein said inorganic substances powder that contains the lithium ion conducting crystal comprises the following material in mole %:
Li 2O 12-18％
Al 2O 3+Ga 2O 3 5-10％
TiO 2+GeO 2 35-45％
SiO 21-10% and
P 2O 5 30-40％。
8. according to each described solid electrolyte of claim 1 to 6, the wherein said inorganic substances powder that contains the lithium ion conducting crystal comprises the following material in quality %:
Li 2O 3-10％
Al 2O 3+Ga 2O 3 5-20％
TiO 2+GeO 2 25-40％
SiO 20.5-8% and
P 2O 5 40-55％。
9. according to each described solid electrolyte of claim 1 to 8, wherein said interpolation polymer inorganic or organic lithium salt has 10 -8Scm -1Ionic conductivity and be to be contained in the described solid electrolyte in the amount with 5-40 quality %.
10. solid electrolyte, it comprises lithium ion conducting glass-ceramic powder and adds the organic polymer of inorganic or organic lithium salt and do not contain electrolytic solution, selects in the group that described organic polymer is made up of copolymer, cross-linked structure thing and its mixture of poly(ethylene oxide) and other one or more organic polymer.
It is high 11. solid electrolyte according to claim 10, its thickness surpass 20 μ m to 60 μ m.
12. according to claim 10 or 11 described solid electrolytes, wherein said lithium ion conducting glass-ceramic powder has 10 -4Scm -1Or higher ionic conductivity and 9 μ m or lower mean particle diameter, and be to be contained in the described solid electrolyte in the amount with 50-95 quality %.
13. according to each described solid electrolyte of claim 10 to 12, it has 10 -5Scm -1Or higher ionic conductivity.
14. according to each described solid electrolyte of claim 10 to 13, wherein said lithium ion conducting glass-ceramic powder has Li 1+x+yAl xTi 2-xSi yP 3-yO 12Crystal mutually as main crystal phase, wherein x and y are 0≤x≤1 and 0≤y≤1.
15. according to each described solid electrolyte of claim 10 to 14, wherein said lithium ion conducting glass-ceramic powder comprises the following material in mole %:
Li 2O 12-18％
Al 2O 3+Ga 2O 3 5-10％
TiO 2+GeO 2 35-45％
SiO 21-10% and
P 2O 5 30-40％。
16. according to each described solid electrolyte of claim 10 to 14, wherein said lithium ion conducting glass-ceramic powder comprises the following material in quality %:
Li 2O 3-10％
Al 2O 3+Ga 2O 3 5-20％
TiO 2+GeO 2 25-40％
SiO 20.5-8% and
P 2O 5 40-55％。
17. according to each described solid electrolyte of claim 10 to 16, wherein said interpolation polymer inorganic or organic lithium salt has 10 -8Scm -1Ionic conductivity and be to be contained in the described solid electrolyte in the amount with 5-40 quality %.
18. a lithium rechargeable battery, it comprises according to each described solid electrolyte of claim 1 to 17.
19. lithium rechargeable battery according to claim 18, it is included in the inorganic substances that contain the lithium ion conducting crystal in positive electrode and/or the negative electrode.
20. lithium rechargeable battery according to claim 19, the contained inorganic substances that contain described lithium ion conducting crystal do not contain hole or the crystal grain boundary that hinders ionic conduction in wherein said positive electrode and/or the described negative electrode.
21. according to claim 19 or 20 described lithium rechargeable batteries, the contained inorganic substances that contain described lithium ion conducting crystal are the lithium ion conducting glass-ceramic in wherein said positive electrode and/or the described negative electrode.
22. according to each described lithium rechargeable battery of claim 19 to 21, in wherein said positive electrode and/or the described negative electrode particle diameter of the contained inorganic substances that contain described lithium ion conducting crystal be described positive electrode and/or described negative electrode active material particle diameter 1/5th or lower.
23. according to each described lithium rechargeable battery of claim 19 to 22, the contained inorganic substances that contain described lithium ion conducting crystal are that amount with the 2-35 quality % of the described active material of the described positive electrode that comprises described inorganic substances and/or described negative electrode exists in wherein said positive electrode and/or the described negative electrode.
24. according to each described lithium rechargeable battery of claim 19 to 23, the contained inorganic substances that contain described lithium ion conducting crystal comprise the following material in mole % in wherein said positive electrode and/or the described negative electrode:
Li 2O 12-18％
Al 2O 3+Ga 2O 3 5-10％
TiO 2+GeO 2 35-45％
SiO 21-10% and
P 2O 5 30-40％。
25. according to each described lithium rechargeable battery of claim 19 to 23, the contained inorganic substances that contain described lithium ion conducting crystal comprise the following material in quality % in wherein said positive electrode and/or the described negative electrode:
Li 2O 3-10％
Al 2O 3+Ga 2O 3 5-20％
TiO 2+GeO 2 25-40％
SiO 20.5-8% and
P 2O 5 40-55％。
26. according to each described lithium rechargeable battery of claim 19 to 25, the inorganic substances that contain described lithium ion conducting crystal contained in wherein said positive electrode and/or the described negative electrode have Li 1+x+yAl xTi 2-xSi yP 3-yO 12Crystal mutually as main crystal phase, wherein x and y are 0≤x≤1 and 0≤y≤1.
27. lithium rechargeable battery according to claim 18, it comprises glass-ceramic and the organic polymer identical with contained person in the described solid electrolyte in described positive electrode and described negative electrode.
CNA2005800352315A 2004-08-17 2005-08-09 Lithium ion secondary battery and a solid electrolyte thereof Pending CN101040401A (en)

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