CN109004179A - All-solid-state battery system and its manufacturing method - Google Patents

All-solid-state battery system and its manufacturing method Download PDF

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Publication number
CN109004179A
CN109004179A CN201810887814.XA CN201810887814A CN109004179A CN 109004179 A CN109004179 A CN 109004179A CN 201810887814 A CN201810887814 A CN 201810887814A CN 109004179 A CN109004179 A CN 109004179A
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active material
electrode active
solid
negative electrode
state battery
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CN201810887814.XA
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CN109004179B (en
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大泷光俊
大森敬介
尾濑德洋
长谷川元
芳贺健吾
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Toyota Motor Corp
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Toyota Motor Corp
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H02J7/0068—Battery or charger load switching, e.g. concurrent charging and load supply
    • H—ELECTRICITY
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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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    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to all-solid-state battery system and its manufacturing methods.The all-solid-state battery system has with positive electrode active material layer (2), the all-solid-state battery of solid electrolyte layer (3) and negative electrode active material layer (4) and to all-solid-state battery using when the control device that is controlled of charging/discharging voltage, wherein, there is alloy system negative electrode active material particle in negative electrode active material layer, the amorphous rate of alloy system negative electrode active material particle is 27.8~82.8%, and meet following conditions: control discharge capacity (mAh)/alloy system negative electrode active material particle theoretical capacity (mAh/g) × alloy system negative electrode active material particle total weight (g) × amorphous rate (%)≤0.60 of 0.32≤all-solid-state battery.In addition, the manufacturing method is included the lamination process of positive electrode active material layer, solid electrolyte layer and the negative electrode active material layer stacking with alloy system negative electrode active material particle, and charges to the initial charge process of the initial charge voltage higher than charging/discharging voltage.

Description

All-solid-state battery system and its manufacturing method
The application be the applying date be September in 2016 14, application No. is 201610827031.3, it is entitled " complete solid The divisional application of the application for a patent for invention of body battery system and its manufacturing method ".
Technical field
The present invention relates to all-solid-state battery system and its manufacturing methods.
Background technique
Currently, in various batteries, from the viewpoint of energy density height, lithium ion battery just attracts attention.Wherein, will The all-solid-state battery that electrolyte is replaced into solid electrolyte just has received special attention.This is because all-solid-state battery and use are electrolysed The secondary cell of liquid is different, and electrolyte is solid, and battery is only made of solid.Therefore, point of such as electrolyte does not occur for presumption Solution etc., and cycle characteristics and energy density are got higher.As usually used negative electrode active material in lithium ion battery, can enumerate Carbon-based negative electrode active material as graphite, soft carbon or hard carbon.In recent years, carbon system electrode, the alloy system bigger to capacity are substituted Negative electrode active material is studied.As an example, silicon, tin, germanium, aluminium etc. can be enumerated.Wherein, especially because capacity is big, because This silicon particle just has received special attention.
It is known that using alloy system negative electrode active material as the battery of negative electrode active material and using carbon-based negative electrode living Property substance etc. is compared as the battery of negative electrode active material, and cycle characteristics is low.As its reason, can enumerate: alloy system cathode is living Property material particle expand and shrink during charge and discharge, thus alloy system negative electrode active material particle is pulverized；In addition, due to Gap, the inside electricity of all-solid-state battery are generated between alloy system negative electrode active material particle and other negative electrode active material layer materials Resistance increases.
In patent document 1, for using silicon particle to pass through tune as the all-solid-state battery of alloy system negative electrode active material The volume change for saving the silicon particle as caused by charge and discharge makes crushing and silicon particle and the other negative electrode active material layers of silicon particle The gap generated between material is reduced, and the increase of the internal resistance of all-solid-state battery is thereby inhibited.
In addition, in patent document 2, disclosing the total solids for using silicon particle as alloy system negative electrode active material Battery carries out initial charge/discharge, i.e. in the early stage only once lower than long-time charging is carried out under usual voltage, thus makes silicon grain Son activates and improves utilization rate, in addition, making the side of the interface good bond of silicon particle and other negative electrode active material layer materials Method.
Existing technical literature
Patent document
Patent document 1: special open 2014-086218 bulletin
Patent document 2: special open 2014-041783 bulletin
Summary of the invention
Problems to be solved by the invention
Alloy system negative electrode active material particle is used to have as the all-solid-state battery of negative electrode active material because of following reason Have the problem that cycle characteristics is low: alloy system negative electrode active material particle is expanded and is shunk during charge and discharge, and thus alloy system is negative Pole active material particle is pulverized；In addition, alloy system negative electrode active material particle and other negative electrode active material layer materials it Between generate gap.
Therefore, in order to solve the above problems, a kind of raising is needed to use alloy system negative electrode active material particle as negative The method of the cycle characteristics of the all-solid-state battery of pole active material.As specific method, as described in Patent Document 1, such as make Use silicon particle as in the case where alloy system negative electrode active material particle, it is contemplated that come by adjusting the volume change of silicon particle Resistance is reduced, so that cycle characteristics be made to improve.
But even if the drop of cycle characteristics is still seen in the case where adjustment volume change as described in Patent Document 1 It is low.A possibility which imply the not only crushing of the silicon particle caused by the expansion of silicon particle and contraction, but also imply and carry out A possibility that certain chemical deteriorations.
The technology that therefore, it is necessary to further increase cycle characteristics.
That is, the main purpose of the present invention is to provide a kind of all-solid-state battery systems and its manufacture that cycle characteristics improves Method.
Means for solving the problems
1. all-solid-state battery system has with positive electrode active material layer, solid electrolyte layer and negative electrode active material The all-solid-state battery of layer and to all-solid-state battery using when the control device that is controlled of charging/discharging voltage, wherein cathode There is alloy system negative electrode active material particle, the amorphous rate of alloy system negative electrode active material particle is 27.8 in active material layer ~82.8%, and meet following conditions:
0.32≤Z/W≤0.60,
Z: the control discharge capacity (mAh) of all-solid-state battery,
W: theoretical capacity (mAh/g) × alloy system negative electrode active material particle of alloy system negative electrode active material particle is complete Portion's weight (g) × amorphous rate (%).
2. the all-solid-state battery system recorded in above-mentioned 1, wherein alloy system negative electrode active material particle is silicon particle.
3. the all-solid-state battery system recorded in above-mentioned 1 or 2, wherein all or part of positive active material is at least A part is coated with protective coating, which is the metal oxide containing lithium.
4. the all-solid-state battery system recorded in above-mentioned 3, wherein the metal oxide containing lithium of protective coating is niobic acid Lithium.
5. the all-solid-state battery system recorded in above-mentioned 1~4 any one, wherein control device controls charging/discharging voltage In the range of 2.50V or more 4.40V or less.
6. the manufacturing method of all-solid-state battery system, which has with positive electrode active material layer, admittedly The all-solid-state battery of body electrolyte layer and negative electrode active material layer and charging/discharging voltage when using all-solid-state battery carry out The control device of control, the method comprising: by positive electrode active material layer, solid electrolyte layer and there is alloy system negative electrode active material The lamination process of the negative electrode active material layer stacking of plasmid, and all-solid-state battery charged to initial higher than charging/discharging voltage The initial charge process of charging voltage.
7. the method recorded in above-mentioned 6, wherein alloy system negative electrode active material particle is silicon particle.
8. the method recorded in above-mentioned 6 or 7, wherein charging/discharging voltage in the range of 2.50V or more 4.40V or less, and And in initial charge process, initial charge voltage is greater than 4.45V and 5.00V or less.
9. the method recorded in above-mentioned any one of 6~8, wherein positive electrode active material layer, which has, is coated with protective coating Positive active material, the protective coating be the metal oxide containing lithium.
10. the method recorded in above-mentioned 9, wherein the metal oxide containing lithium of protective coating is lithium niobate.
11. the method recorded in above-mentioned 9 or 10, wherein carry out initial charge process in a manner of meeting following conditions:
(charge volume (Q) is to the change rate (dQ/dV) of the voltage (V) in upper limit charging voltage/(fill in initial charge process The average value of charge volume (Q) when piezoelectric voltage is 4.00V or more 4.40V or less to the change rate (dQ/dV) of voltage (V)) > 1.3。
Invention effect
According to the present invention, it is possible to provide a kind of all-solid-state battery system and its manufacturing method that cycle characteristics improves.
Detailed description of the invention
Fig. 1 is the figure of an example of diagram all-solid-state battery system of the invention.
Fig. 2 is the figure of an example of all-solid-state battery used in diagram all-solid-state battery system of the invention.
Fig. 3 is the figure of an example of all-solid-state battery used in diagram all-solid-state battery system of the invention.
Fig. 4 is the figure of an example of all-solid-state battery used in diagram all-solid-state battery system of the invention.
Fig. 5 is the figure for illustrating the working principle of the manufacturing method of the present invention.
Fig. 6 is to show the figure of the relationship of amorphous rate and initial charge amount.
Description of symbols
1 positive electrode collector, 2 positive electrode active material layer, 3 solid electrolyte layer, 4 negative electrode active material layer, 5 cathode 6 all-solid-state battery of collector
Specific embodiment
Embodiments of the present invention are described in detail below.It is explained, the present invention is not limited to the following embodiments and the accompanying drawings, can Carry out various modifications in the range of the purport of the present invention to implement.
" all-solid-state battery system of the invention "
All-solid-state battery system of the invention has with positive electrode active material layer, solid electrolyte layer and negative electrode active material The all-solid-state battery of matter layer and to all-solid-state battery using when the control device that is controlled of charging/discharging voltage, wherein it is negative There is alloy system negative electrode active material particle, the amorphous rate of alloy system negative electrode active material particle is in the active material layer of pole 27.8~82.8%, and meet following conditions:
0.32≤Z/W≤0.60,
Z: the control discharge capacity (mAh) of all-solid-state battery,
W: theoretical capacity (mAh/g) × alloy system negative electrode active material particle of alloy system negative electrode active material particle is complete Portion's weight (g) × amorphous rate (%).
In the formula, the control discharge capacity Z of all-solid-state battery refers to the all-solid-state battery system when completing as product By the discharge capacity in the practical voltage range controlled of control device in system.
In other words, in the formula, the control discharge capacity Z of all-solid-state battery is actually indicated by by control device control Electric discharge in the voltage range of system, the all-solid-state battery of completion is in initial charge and discharge (i.e. charge and discharge when initially conventional use) In the amount of lithium that can release.
In the formula, the theoretical capacity (mAh/g) of alloy system negative electrode active material particle refers to from alloy system negative electrode active Material particle occludes amount of electrons n (mol), Faraday constant F (C/mol) and the molecular weight M (g/mol) when the maximum amount of lithium, makes With the calculated value of nF/M formula.
In other words, the theoretical capacity W of alloy system negative electrode active material particle actually indicates alloy system negative electrode active material The total amount of acceptable lithium on the decrystallized part of theory of plasmid.
Therefore, which is stored in negative electrode active material layer and can be released by electric discharge after actually indicating battery charging Lithium amount less than acceptable lithium on the decrystallized part of theory in alloy system negative electrode active material particle total amount, and In a certain range.
In the case where the value of Z/W is less than 0.32, energy density reduces, and the performance as battery declines.On the other hand, exist In the case that the value of Z/W is more than 0.60, when to all-solid-state battery charge and discharge, it is believed that alloy system negative electrode active material particle Decrystallized part increases relative to the ratio of expansion and the crystalline part for the alloy system negative electrode active material particle shunk, and closes Gold system negative electrode active material particle stress and be readily broken.
It is explained, the lower limit of Z/W can be 0.33 or more, 0.35 or more, 0.37 or more, 0.40 or more, 0.42 or more Or 0.45 or more, the upper limit can be 0.58 or less, 0.55 or less, 0.53 or less, 0.50 or less or 0.48 or less.
By meeting such condition, all-solid-state battery of the invention can realize high cycle characteristics.Fig. 1 is to illustrate this hair The figure of an example of bright all-solid-state battery system.All-solid-state battery system of the invention has all-solid-state battery 6 and to complete solid Body battery using when the control device 100 that is controlled of charging/discharging voltage.
It is not limited by theory, but is believed that the improvement of the cycle characteristics of all-solid-state battery system of the invention is sent out as follows It is raw.
To used alloy system negative electrode active material particle as negative electrode active material lithium ion secondary battery carry out When initial charge, the lithium ion released from positive active material is reacted with alloy system negative electrode active material particle, generates alloy system The alloy of negative electrode active material and lithium.In the reaction, the crystalline structure collapses in alloy system negative electrode active material particle, with The alloy system negative electrode active material that lithium is reacted is decrystallized.In turn, when being discharged from the state, the alloy system cathode The alloy of active material and lithium reverts to alloy system negative electrode active material because releasing lithium in the form of lithium ion, but the alloy It is that the decrystallized part of negative electrode active material can not restore the structure of the crystalline to initial charge, but maintain decrystallized The state of structure.Moreover, mainly the part for becoming amorphous is reacted with lithium ion and forms conjunction in charging behind The alloy of gold system negative electrode active material and lithium.
Initial to having used all-solid-state battery of the alloy system negative electrode active material particle as negative electrode active material to carry out In the case where charging, which is not in whole alloy system negative electrode active material particles but only in alloy system cathode Occur in a part of active material particle, the state of crystalline is not reacted and remained to other parts with lithium.
Previous all-solid-state battery is since the decrystallized part of alloy system negative electrode active material particle is few, in charge and discharge Amorphous fraction and lithium preferential reaction, thus locally expand contraction in decrystallized a part when electric.Therefore, decrystallized Partial volume expansion shrinking percentage increases.Therefore, a part of alloy system negative electrode active material particle is anti-because of repeated charge Compound expansion and contraction, due to the part reacted with lithium ion and form alloy in alloy system negative electrode active material particle and not with The stress etc. that lithium ion reaction generates between the part without forming alloy, alloy system negative electrode active material particle are pulverized.
On the other hand, in the present invention, by increasing decrystallized part, prevent lithium from locally reacting, make decrystallized The reacting dose at partial each position and lithium is reduced, and thus can reduce the cubical expansivity of decrystallized part.It is applied to as a result, The stress of alloy system negative electrode active material particle reduces, and inhibits the crushing of alloy system negative electrode active material particle, to can be improved The cycle characteristics of all-solid-state battery.In addition also speculate there is following possibility: due to the change of the cubical expansivity of decrystallized part Change, it is suppressed that the progress of chemical deterioration.
In addition, the amorphous rate of alloy system negative electrode active material particle is 27.8~82.8%.
It is believed that compared with alloy system negative electrode active material particle is all decrystallized, alloy system negative electrode active material particle In a part when being crystalline, the cycle characteristics of all-solid-state battery improves.This is regarded as due to alloy system negative electrode active material Crystalline part in plasmid becomes core, to make the structure stabilization of particle entirety.
< positive electrode active material layer >
Positive electrode active material layer in the present invention has positive active material, and optionally there is adhesive, conduction to help Agent and solid electrolyte.
As a positive electrode active material, as long as the material that the cathode active material that can be used as lithium secondary battery uses It is not particularly limited.For example, it is brilliant to enumerate cobalt acid lithium, lithium nickelate, nickle cobalt lithium manganate, LiMn2O4, xenogenesis element substitution Li-Mn point Stone, lithium titanate or by LiMPO4The phosphate metal lithium etc. for the composition that (M is selected from one or more of Fe, Mn, Co, Ni) indicates, Or their combination.
Positive active material can also be coated with protective coating, which is the gold containing lithium with lithium as ingredient Belong to oxide.Oxide envelope is formed this prevents positive active material and solid electrolytic qualitative response, and anode can be prevented The deterioration of active material.
As the metal oxide containing lithium, as long as having lithium-ion-conducting and even if with positive active material or admittedly The contact of body electrolyte can also maintain the substance of the form of immobilising coating to be just not particularly limited.For example, lithium niobate can be used (LiNbO3), lithium titanate (Li4Ti5O12) or lithium phosphate (Li3PO4) etc..
As solid electrolyte, it is able to use the sulfide solid electrolysis that can be used as the solid electrolyte of all-solid-state battery Matter.For example, Li can be enumerated2S-SiS2、LiI-Li2S-SiS2、LiI-Li2S-P2S5、LiI-Li3PO4-P2S5、Li2S-P2S5Deng.
It as adhesive, is not particularly limited, but can enumerate: fluoropolymer resin, such as Kynoar (PVDF), polytetrafluoro Ethylene (PTFE), polyimides (PI), polyamide (PA), polyamide-imides (PAI), butadiene rubber (BR), butadiene-styrene rubber (SBR), nitrile rubber (NBR), styrene-ethylene-butylene-styrene block copolymer (SEBS) or carboxymethyl cellulose Or their combination (CMC) etc..
As conductive auxiliary agent, in addition to VGCF, acetylene black, Ketjen black, carbon nanotube (CNT) or carbon nano-fiber (CNF) etc. Other than carbon material, the metals such as nickel, aluminium, SUS or their combination can be also enumerated.
< solid electrolyte layer >
Solid electrolyte layer is using the electrolyte recorded in above-mentioned positive electrode active material layer.The thickness of solid electrolyte layer Degree is, for example, 0.1 μm or more 300 μm hereinafter, especially can be 0.1 μm or more 100 μm or less.
< negative electrode active material layer >
Negative electrode active material layer is with negative electrode active material and optionally with conductive auxiliary agent, adhesive and solid electrolytic Matter.
As negative electrode active material, alloy system negative electrode active material particle can be used.Here, in the present invention, alloy system Negative electrode active material, which refers to, to be reacted in cell reaction with lithium to form the metal system negative electrode active material of amorphous alloy.It closes Gold system negative electrode active material particle is not particularly limited, but can for example enumerate silicon particle, tin particle, germanium particle, aluminum particulate or they Combination.The primary particle size (median particle diameter) of alloy system negative electrode active material particle is preferably 10 μm or less, 7 μm or less, 5 μm with It is lower or 3 μm or less.Here, the primary particle size (median particle diameter) of negative electrode active material particle uses laser diffraction and scattering type partial size Distribution measurement device LA-920 (hole field production made) is measured.
In the alloy system negative electrode active material particle that the all-solid-state battery for all-solid-state battery system of the invention has In, a part of particle is amorphous.The decrystallized of the alloy system negative electrode active material particle for example can be by complete solid in assembling The initial charge/discharge that is carried out after body battery carries out.
The amorphous rate of alloy system negative electrode active material particle is 27.8~82.8%.The amorphous rate can for 30% with Above, 35% or more, 40% or more or 50% or more, it can be 80% or less, 75% or less, 70% or less, 65% or less, 60% Below or 55% or less.Here, amorphous rate refers to decrystallized part relative to whole alloy system negative electrode active material particles Ratio.
It such as can be used as following ratio to calculate the amorphous rate: being carried out applying assigned voltage to all-solid-state battery After charged and discharged to 2.5V, in negative electrode active material layer, for the position using 5 μm away from solid electrolyte layer~15 μm TEM measure and the visual field of 10 μm of 10 μ m that determines present in more than at least four particle alloy system negative electrode active material Particle (includes a part of alloy system negative electrode active material particle, is not necessarily required to it can be seen that alloy system negative electrode active material The all images of particle), the area of the decrystallized part in alloy system negative electrode active material particle is calculated relative to by BF The ratio of the area for the alloy system negative electrode active material particle that image is confirmed；Using the ratio as amorphous rate.
As conductive auxiliary agent, adhesive and solid electrolyte, those of record in above-mentioned positive electrode active material layer can be used.
< control device >
Charging/discharging voltage when control device used in all-solid-state battery system of the invention uses all-solid-state battery It is controlled.Control device is not particularly limited as long as the device that can be controlled charging/discharging voltage.Control device is for example There can be following function: in all-solid-state battery electric discharge, judge whether the voltage of all-solid-state battery reaches certain voltage, and Terminate electric discharge in the case where reaching certain voltage；And in all-solid-state battery charging, judge the voltage of all-solid-state battery Whether reach certain voltage, and terminates charging in the case where reaching certain voltage.
Voltage when control device preferably uses all-solid-state battery controls in the range of 2.50V or more 4.40V or less. This is because in the case where being discharged to the voltage less than 2.50V, or in the case where charging to the voltage greater than 4.40V, Positive active material or negative electrode active material deterioration, battery performance decline.In addition, the discharge voltage controlled may range from 2.60V or more, 2.70V or more, 2.90V or more, 3.00V or more, 3.10V or more or 3.20V or more, can for 4.30V or less, 4.20V or less, 4.10V or less, 4.00V or less, 3.90V or less, 3.80V or less, 3.70V or less, 3.60V or less, 3.50V with Under, 3.40V or less or 3.30V or less.
The configuration example > of < all-solid-state battery used in all-solid-state battery system of the invention
As the specific composition example of the all-solid-state battery 6 used in all-solid-state battery system of the invention, can enumerate by Sequence has positive electrode collector 1, positive electrode active material layer 2, solid electrolyte layer 3, negative electrode active material layer 4 and negative electrode collector 5 composition (referring to Fig. 2).
In addition, as shown in figure 3, the all-solid-state battery used in all-solid-state battery system of the invention is also possible to negative Centered on electrode current collector, there is negative electrode active material layer, solid electrolyte layer, positive electrode active material layer and anode collection in its two sides The composition of electric body.
In addition, as shown in figure 4, the all-solid-state battery used in all-solid-state battery system of the invention is also possible to just Centered on electrode current collector, there is positive electrode active material layer, solid electrolyte layer, negative electrode active material layer and cathode collection in its two sides The composition of electric body.
It is explained, the purport of Fig. 2~4, which is not lain in, is limited in total solids used in all-solid-state battery system of the invention The composition of battery.
" manufacturing method of all-solid-state battery system of the invention "
The manufacturing method of all-solid-state battery system of the invention is the method with following process: by positive active material Layer, solid electrolyte layer and the negative electrode active material layer layer with alloy system negative electrode active material particle as negative electrode active material Folded lamination process；With charged to after lamination process higher than battery using when charging/discharging voltage charging voltage initially fill Electrician's sequence.
It is not limited, but is thought working principle of the present invention is as follows described by principle.
Alloy system negative electrode active material particle a part due to charging react with lithium forming alloy.Then, shape It is still decrystallized state even if being released after lithium ion because of electric discharge at the part of alloy.
By carrying out initial charge in the case where being higher than as the voltage of the use scope of battery product, and use as product Situation is compared, and more lithium ions can be mobile to negative side, is reacted with alloy system negative electrode active material particle.As a result, with The lithium ion of positive active material in is released capacity and is compared, and can increase in alloy system negative electrode active material particle Decrystallized part, the lithium ion that cathode can be improved receive capacity.
In turn, the inventors discovered that, due to making more lithium ions and alloy system negative electrode active material in initial charge Particle reaction, therefore the positive active material for being coated with protective coating can be used in positive active material, which is niobic acid The metal oxide containing lithium such as lithium.
The metal oxide containing lithium for such protective coating is under the voltage for being higher than common battery use scope Release lithium ion.It therefore, can with positive active material by charging under the voltage for being higher than common battery use scope The amount of releasing is compared, and can release more lithium ions to negative side.It can make more alloy system negative electrode active material particles as a result, It is reacted with lithium ion, can further improve the amorphous rate of alloy system negative electrode active material particle.
It is explained, in the case where so carrying out charge and discharge under the voltage for being higher than common battery use scope, just The deterioration of pole active material, positive active material occlude the ability decline for releasing lithium ion.But it is closed due to can further improve The amorphous rate of gold system negative electrode active material particle, therefore improved as the cycle characteristics of battery entirety.
< lamination process >
Lamination process is that by positive electrode active material layer, solid electrolyte layer and there is alloy system negative electrode active material particle to make The process being laminated for the negative electrode active material layer of negative electrode active material.The positive electrode active material layer used in lamination process is consolidated Body electrolyte layer, negative electrode active material layer and alloy system negative electrode active material particle can be used and in all-solid-state batteries of the invention Used in positive electrode active material layer, solid electrolyte layer, negative electrode active material layer and alloy system negative electrode active material particle it is same The substance of sample.In addition, all or part of for the positive active material for including in positive electrode active material layer can be coated with containing lithium The protective coating of the metal oxide containing lithium as ingredient.It as the metal oxide containing lithium, is not particularly limited, but for example may be used Enumerate lithium niobate.
< initial charge process >
In initial charge process, pass through the lithium ion and alloy system negative electrode active material for making to release from positive active material Particle reaction makes the decrystallized progress of alloy system negative electrode active material.
Initial charge voltage in initial charge process is to fill higher than what is controlled in the all-solid-state battery system of manufacture The voltage of discharge voltage.For example, being controlled in the range of 2.50V or more 4.40V or less when manufacture is scheduled to charging/discharging voltage In the case where all-solid-state battery system, initial charge voltage may be selected to be greater than 4.45V and 5.00V the following value.
Additionally, it is preferred that being charged in a manner of meeting following conditions.
(change rate (dQ/dV) of the charge volume (Q) to the voltage (V) of charging voltage)/(charging voltage is 4.00V or more The average value of charge volume (Q) when 4.40V or less to the change rate (dQ/dV) of voltage (V)) > 1.3.
It is explained, (change rate (dQ/dV) of the charge volume (Q) to the voltage (V) of charging voltage)/(charging voltage is The average value of charge volume (Q) when 4.00V or more 4.40V or less to the change rate (dQ/dV) of voltage (V)) can for 1.4 with Above, 1.5 or more, 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, 2.0 or more or 2.1 or more.
Above-mentioned formula is illustrated using Fig. 5.All-solid-state battery is being charged to the charge and discharge controlled by control device In the case where the range of voltage, main that releasing of the lithium ion from positive active material occurs, charge volume (Q) is with voltage (V) Rise and increases ((range 10) of Fig. 5).When keeping the charging voltage of all-solid-state battery further up, under certain voltage, hair Raw lithium ion is from the releasing in the protective coating of the metal oxide containing lithium, therefore the lithium ion mobile to negative side from positive side Total amount increase, charge volume (Q) increases ((range 20) of Fig. 5) to the change rate (dQ/dV) of voltage (V).
It is explained, in order to further increase the cycle characteristics of all-solid-state battery, can take and be replaced after initial charge process The method for changing positive electrode active material layer.This method can for example pass through progress of such as getting off: after initial charge process, from having anode Active material layer, solid electrolyte layer and the negative electrode active with alloy system negative electrode active material particle as negative electrode active material The laminated body of material layer removes positive electrode active material layer or positive electrode active material layer and solid electrolyte layer, by the anode of new production Active material layer or positive electrode active material layer and solid electrolyte layer are laminated in alloy system negative electrode active material particle conduct The negative electrode active material layer of negative electrode active material.
By the additional process, will be replaced with newly due to the positive electrode active material layer for having carried out initial charge process and having deteriorated Positive electrode active material layer, can further improve the performance of battery.In addition, due to premised on replacing positive electrode active material layer, Therefore the deterioration of positive electrode active material layer in initial charge process can not be considered to carry out the charge and discharge under high voltage.
In addition, preferably being replaced in the case where being replaced the method for positive electrode active material layer after initial charge process The lithium content that positive electrode active material layer before changing can release is greater than the lithium content that replaced positive electrode active material layer can release.
It is explained, it is living that the lithium ion content that the positive electrode active material layer before replacement can release is greater than replaced anode Property the lithium content that can release of material layer in the case where, the voltage in initial charge process can not also be made to be greater than by control device institute The range of the charging/discharging voltage of control.This is because in the case where charging voltage is equal, what positive electrode active material layer can release Lithium content is more, then the amount for the lithium ion that positive electrode active material layer is released is more.
By using such composition, in initial charge process, due to can will be than replaced positive electrode active material layer The more lithium ions of the lithium ion that can be released are supplied to negative electrode active material layer, therefore can further improve alloy system negative electrode active The amorphous rate of material particle.
Embodiment
" Examples 1 to 3 and the Comparative Examples 1 to 5 "
As described below, the all-solid-state battery for making Examples 1 to 3 and the Comparative Examples 1 to 5, evaluates its battery performance.
1 > of < embodiment
It operates as described below, make the all-solid-state battery of embodiment 1 and evaluates its battery performance.
1. the production of all-solid-state battery
(1) production of positive electrode active material layer
By the 5wt% butyl butyrate dissolved with the butyl butyrate as decentralized medium, the Kynoar as adhesive Solution is coated with the LiNi as a positive electrode active material of the lithium niobate as protective coating1/3Co1/3Mn1/3O2, as solid The Li of electrolyte2S-P2S5Series vitro-ceramic, and VGCF (vapor phase method carbon fiber) the addition polypropylene system appearance as conductive auxiliary agent In device, stirred 30 seconds with ultrasonic wave distributing device (エ ス エ system テ ー system, ProductName UH-50).Thereafter, with oscillator (bavin field Scientific Co. Ltd. system, ProductName TTM-1) polypropylene container is vibrated 3 minutes, then 30 are stirred with ultrasonic wave distributing device Second, production positive electrode active material layer paste.
Using applicator (applicator), uses paste to be coated in as anode positive electrode active material layer using scraper method and collect It is 30 minutes dry on the hot plate for be heated to 100 DEG C thereafter on the aluminium foil of electric body, thus make positive electrode active material layer.
(2) production of negative electrode active material layer
By the 5wt% butyl butyrate dissolved with the butyl butyrate as decentralized medium, the Kynoar as adhesive Solution, the Li as the silicon particle (high purity length of schooling) of negative electrode active material, as solid electrolyte2S-P2S5It is glass pottery Porcelain, and as in VGCF (vapor phase method carbon fiber) the addition polypropylene container of conductive auxiliary agent, stirred with ultrasonic wave distributing device It mixes 30 seconds.Thereafter, polypropylene container is vibrated 30 minutes with oscillator, production negative electrode active material layer paste.
Using applicator, paste is used to be coated in as the copper foil of negative electrode collector negative electrode active material layer using scraper method On, it is 30 minutes dry on the hot plate for be heated to 100 DEG C thereafter, thus make negative electrode active material layer.
(3) production of solid electrolyte layer
By the 5wt% n-heptane solution dissolved with the heptane as decentralized medium, the butadiene rubber as adhesive, and Li containing the lithium iodide as solid electrolyte2S-P2S5Series vitro-ceramic is added in polypropylene container, is dispersed with ultrasonic wave Device stirs 30 seconds.Thereafter, polypropylene container is vibrated 30 minutes with oscillator, production solid electrolyte layer paste.
Using applicator, uses paste to be coated in as on the aluminium foil of substrate solid electrolyte layer using scraper method, exist thereafter Drying 30 minutes on 100 DEG C of hot plate have been heated to, solid electrolyte layer is thus made.
(4) stacking and suppression process
Solid electrolyte layer is laminated in positive electrode active material layer, so that solid electrolyte layer and positive electrode active material layer phase It connects, with 1 ton/cm2It is suppressed, removes the aluminium foil of the substrate as solid electrolyte layer, production solid electrolyte layer and anode The laminated body of active material layer.
Thereafter, negative electrode active material layer is overlapped to the solid electrolyte layer side of the laminated body, with 6 tons/cm2It is pressed System, completes battery.The unit (cell) of production is constrained with the confining pressure of 2Nm using constraint fixture, is put into drier In evaluated.
2. Cell Performance Evaluation
For the all-solid-state battery of the embodiment 1 of production, permanent electricity is carried out with 10 hour rates (1/10C) as initial charge Stream-constant voltage charges to 4.55V (terminating electric current 1/100C), is put as initial discharge with constant current-constant voltage discharge mode Electricity is to 2.50V.Thereafter, it carries out constant current-constant voltage and charges to 4.40V (terminating electric current 1/100C), with constant current-constant voltage Discharge mode is discharged to 2.50V, measures discharge capacity of the all-solid-state battery of embodiment 1 before endurance test.
Thereafter, as endurance test, 300 following circulations is repeated: 4.17V is being charged to 0.5 hour rate (2C) Later, it is discharged to 3.17V.After endurance test, carries out constant current-constant voltage and charge to 4.40V (terminating electric current 1/100C), with Constant current-constant voltage discharge mode is discharged to 2.50V, measures electric discharge of the all-solid-state battery of embodiment 1 after endurance test and holds Amount.
The discharge capacity before discharge capacity/endurance test after calculating endurance test calculates the total solids electricity of embodiment 1 The capacity maintenance rate in pond.
1~3 > of < embodiment 2,3 and comparative example
The all-solid-state battery of embodiment 2,3 and comparative example 1~3 is made by method similarly to Example 1.Thereafter, it removes The initial charge voltage of embodiment 2 is set as 4.70V, the initial charge voltage of embodiment 3 is set as to 5.00V, by comparative example 1 Initial charge voltage be set as 4.45V, the initial charge voltage of comparative example 2 is set as to 4.40V and by comparative example 3 initially filling Piezoelectric voltage is set as other than 3.60V, and the total solids of embodiment 2,3 and comparative example 1~3 is evaluated by method similarly to Example 1 The battery performance of battery.
The > of < comparative example 4 and 5
In the production of negative electrode active material layer, relative to the thickness of the negative electrode active material layer in embodiment 1, it will pass through The thickness of the negative electrode active material layer of comparative example 4 made by scraper method is set as about 2 times, will pass through comparison made by scraper method The thickness of the negative electrode active material layer of example 5 is set as about 0.5 times, in addition to this, passes through method comparison similarly to Example 1 The all-solid-state battery of example 4 and 5.Thereafter, for comparative example 4 and 5, initial charge voltage is set as 4.45V, in addition to this, is passed through The battery performance of the all-solid-state battery of method evaluation comparison example 4 and 5 similarly to Example 1.
< measurement result >
Manufacturing conditions, the battery structure of the all-solid-state battery of Examples 1 to 3 and the Comparative Examples 1 to 5 are shown in following table 1 And measurement result.
[table 1]
1. the explanation of table 1
In table 1, " Si weight " is that the weight of the silicon particle of negative electrode active material is included as in all-solid-state battery.
In addition, " amorphous rate " is ratio of the decrystallized part relative to whole silicon particles.For the sake of simplicity, pass through 0.031 × " initial charge amount " calculates " amorphous rate " (referring to following " passes of initial charge capacity and amorphous rate System ").
In addition, " amorphous capacity (W) " indicates the capacity of decrystallized part in silicon particle.By " amorphous capacity (W) "= (" Si weight " (mg) × 1000) × " amorphous rate " (%) × 4200 (mAh/g) (theoretical capacity of silicon particle) is " non-to calculate Brilliant capacity (W) ".
In addition, passing through control using the value of the discharge capacity before endurance test as all-solid-state battery system when product completion Discharge capacity in the practical voltage range controlled of device processed finds out " control discharge capacity (Z) ".
In addition, " Z/W " is " control discharge capacity (Z) " divided by value obtained from " amorphous capacity (W) ".
In addition, " capacity maintenance rate " is to count the result of the endurance test of the all-solid-state battery of comparative example 1 as 100% The value of calculating.
2. investigating
" the amorphous rate " of the all-solid-state battery of Examples 1 to 3 is respectively 27.8%, 34.1% and 36.2%, and " Z/ W " is respectively 0.53,0.54 and 0.52.Therefore, the all-solid-state battery of Examples 1 to 3 be all satisfied amorphous rate be 27.8~ 82.8% and 0.32≤Z/W≤0.60.
In the all-solid-state battery of Examples 1 to 3, " capacity maintenance rate " is respectively 108%, 104% and 109%.
" the amorphous rate " of the all-solid-state battery of comparative example 1~4 is respectively 26.6%, 23.9%, 5.8% and 13.3%, And " Z/W " is respectively 0.66,0.68,2.85 and 0.64.Therefore, the all-solid-state battery of comparative example 1~4 is not satisfied decrystallized Rate is 27.8~82.8% and 0.32≤Z/W≤0.60.
In 1~4 all-solid-state battery of comparative example, " capacity maintenance rate " is respectively 100%, 99%, 96% and 97%, than Compared in 2~4 all-solid-state battery of example, compared with the all-solid-state battery of Examples 1 to 3, " capacity maintenance rate " is small.
In addition, " the amorphous rate " of the all-solid-state battery of comparative example 5 is 43.9%, and " Z/W " is 0.67.Therefore, than Compared with the all-solid-state battery of example 5, although to meet amorphous rate be 27.8~82.8%, but is unsatisfactory for 0.32≤Z/W≤0.60.
" capacity maintenance rate " of the all-solid-state battery of comparative example 5 is 97%, compared with the all-solid-state battery of Examples 1 to 3, " capacity maintenance rate " is small.
According to above, it can be said that it is 27.8~82.8% and 0.32≤Z/W≤0.60 that the composition of battery, which meets amorphous rate, All-solid-state battery be unsatisfactory for amorphous rate be 27.8~82.8% and 0.32≤Z/W≤0.60 all-solid-state battery compared with, " capacity maintenance rate " is big.
This indicates that the all-solid-state battery of Examples 1 to 3 " Z/W " compared with comparative example 1 is small, therefore decrystallized part phase Expansion and shrinking percentage for whole silicon particles are less than comparative example 1, and the crushing of the silicon particle as caused by repeated charge is not easy to send out It is raw.
On the other hand, the all-solid-state battery of the Comparative Examples 1 to 5 due to part decrystallized in silicon particle it is insufficient, with Lithium ion reaction increases to the ratio of dilation, and during the charge and discharge for carrying out 300 circulations, silicon particle is because in silicon particle The stress of generation and be crushed, display " capacity maintenance rate " reduce.Particularly, in comparative example 3, " Z/W " is in Examples 1 to 3 With maximum in the Comparative Examples 1 to 5, " capacity maintenance rate " is minimum on the contrary, is 96%.This is indicated in comparative example 3, with charge and discharge Expansion of the decrystallized part relative to whole silicon particles and shrinking percentage increase, compared with other embodiments and comparative example, more More silicon particles is pulverized.
It can thus be assumed that the cycle characteristics of all-solid-state battery can be made into one by charging to higher initial charge voltage Step improves.
" embodiment 4~7 and comparative example 6,7 "
As described below, the all-solid-state battery for making embodiment 4~7 and comparative example 6,7, evaluates its battery performance.
The production of < all-solid-state battery and the evaluation method > of battery performance
By method similarly to Example 1, the all-solid-state battery of embodiment 4~7 and comparative example 6,7 is made.Thereafter, it closes It in embodiment 4, is operated in the same way with the method for embodiment 1, evaluates the battery performance of all-solid-state battery.In addition, in addition to that will implement The initial charge voltage of the all-solid-state battery of example 5~7 and comparative example 6,7 is set as 4.60V for embodiment 5, embodiment 6 is set For 4.65V, it is set as 4.70V for embodiment 7,4.40V is set as comparative example 6, comparative example 7 is set as other than 4.45V, leads to Method similarly to Example 1 is crossed, the battery performance of the all-solid-state battery of embodiment 5~7 and comparative example 6,7 is evaluated.
< measurement result >
The manufacturing conditions of the all-solid-state battery of embodiment 4~7 and comparative example 6,7 are shown in following table 2, battery is constituted and Measurement result.
[table 2]
1. the explanation of table 2
In table 2, " β " is change rate of the capacity (Q) in initial charge process to the voltage (V) in upper limit charging voltage (dQ/dV), the capacity (Q) that " α " is charging voltage when being 4.0V or more 4.4V or less is to the change rate (dQ/dV) of voltage (V) Average value.
It is explained, " the amorphous rate " in table 2 is calculated by " amorphous rate " same method with table 1.
Therefore, " beta/alpha " is (change rate of capacity (Q) in initial charge process to the voltage (V) in upper limit charging voltage (dQ/dV))/(capacity (Q) being averaged to change rate (dQ/dV) of voltage (V) when charging voltage is 4.0V or more 4.4V or less Value).
In table 2, " amorphous capacity " indicates the capacity of decrystallized part in silicon particle.
In table 2, " capacity maintenance rate " is that the result of the endurance test of the all-solid-state battery of comparative example 7 is set as 100% And calculated value.In addition, " resistance " is the internal resistance of all-solid-state battery, but will be in the all-solid-state battery of comparative example 7 Portion's resistance is set as 100% and calculated value.
2. investigating
In the method for embodiment 4~6, all-solid-state battery is carried out in such a way that beta/alpha respectively becomes 1.91,2.18 and 1.65 Production.Therefore, the method for embodiment 4~6 meets beta/alpha > 1.3.
" the amorphous capacity " of the all-solid-state battery made by the method for embodiment 4~6 is respectively 3.40mAh, 3.37mAh And 3.62mAh, compared with the all-solid-state battery made by comparing the method for example 6 and 7, amorphous capacity is big.In addition, passing through implementation " capacity maintenance rate " of the all-solid-state battery of the method production of example 4~6 is respectively 108%, 108% and 106%, is all larger than and compares " capacity maintenance rate " of example 6.In addition, " resistance " is respectively 94%, 93% and 96%, respectively less than " resistance " of comparative example 6.
This is indicated, carrying out initial charge in such a way that beta/alpha is greater than 1.3, can make the big total solids electricity of amorphous capacity Pond, and " capacity maintenance rate " and " resistance " of made all-solid-state battery improves.
In contrast, in the method for comparative example 6 and 7, total solids is carried out in such a way that beta/alpha respectively becomes 1.10 and 1.27 The production of battery.Therefore, the method for comparative example 6 and 7 is unsatisfactory for beta/alpha > 1.3.
" capacity maintenance rate " of the all-solid-state battery made by comparing the method for example 6 and 7 is respectively 96% and 100%. In addition, " resistance " is respectively 101% and 100%.
In addition, carrying out the production of all-solid-state battery in such a way that beta/alpha becomes 0.69 in the method for embodiment 7.
" capacity maintenance rate " of the all-solid-state battery made by the method for embodiment 7 is 106%.In addition, " resistance " is 99%.
In the method for embodiment 7, preparatory progress initial charge to 4.70V, compared with the method for embodiment 4~6, although For high initial charge voltage, but beta/alpha is the value less than 1.3.Although this is regarded as due to as charging voltage improves, from niobium Sour lithium has released lithium ion, but before charging voltage reaches 4.70V, has substantially released the lithium ion that lithium niobate can release, It is reduced from positive side to the mobile lithium ion of negative side.
In addition, the all-solid-state battery of embodiment 7, compared with comparative example 6, " capacity maintenance rate " greatly, " resistance " is small.Another party Face, for the all-solid-state battery of embodiment 7 compared with embodiment 4~6, " resistance " is big.This is regarded as applying due to the protection of lithium niobate The deterioration of layer is big, etc..Therefore, not instead of only improve initial charge voltage can, pass through control initial charge/discharge So that beta/alpha is greater than 1.3, it can just increase " capacity maintenance rate " and reduce " resistance ".
Thus, it can be said that all-solid-state battery can be made controlling initial charge/discharge in such a way that beta/alpha becomes and is greater than 1.3 Cycle characteristics improve.
1~6 > of < reference example
In order to indicate the relationship of the value of beta/alpha and the protective coating of the positive active material based on the metal oxide containing lithium, The all-solid-state battery for making reference example 1~6 as described below, evaluates its battery performance.
1. reference example 1~3
It other than negative electrode active material to be replaced as to natural graphite system carbon, operates similarly to Example 4, production reference The all-solid-state battery of example 1~3.
For the all-solid-state battery of the reference example 1~3 of production, by initial charge voltage for reference example 1 be set as 4.45V, 4.55V is set as reference example 2,4.70V is set as reference example 3, in addition to this, is operated similarly to Example 4, to reference The all-solid-state battery of example 1~3 carries out initial charge, measures beta/alpha.
2. reference example 4~6
It is not coated with the LiNi of lithium niobate in addition to positive active material to be replaced into1/3Co1/3Mn1/3O2And by negative electrode active Substance is replaced as other than natural graphite system carbon, is operated similarly to Example 4, and the all-solid-state battery of reference example 4~6 is made.
For the all-solid-state battery of the reference example 4~6 of production, by initial charge voltage for reference example 4 be set as 4.45V, 4.55V is set as reference example 5,4.70V is set as reference example 6, in addition to this, is operated similarly to Example 4, to reference The all-solid-state battery of example 4~6 carries out initial charge, measures beta/alpha.
3. measurement result
The experiment condition and measurement result of the all-solid-state battery of reference example 1~6 are shown in following Table 3.
[table 3]
1. the explanation of table 3
In table 3, " beta/alpha " is as described in the explanation of table 2.
2. investigating
As described in Table 3, in reference example 1~3, beta/alpha is respectively 1.19,1.77 and 1.52, is greater than 1, in contrast, is joining It examines in example 4~6, beta/alpha is respectively 0.93,0.90 and 0.53, less than 1.This is indicated by making to contain niobium in positive electrode active material layer Sour lithium, it is possible to increase the value of beta/alpha.It, can will be more under high voltage that is, by making to contain lithium niobate in positive electrode active material layer Lithium ion is supplied to negative electrode active material.
" embodiment 8~11 "
As described below, the all-solid-state battery for making embodiment 8~11, evaluates its battery performance.
8 > of < embodiment
1. the manufacturing method of false all-solid lithium secondary battery
(1) the lithium supply production of positive electrode active material layer
By the 5wt% butyl butyrate dissolved with the butyl butyrate as decentralized medium, the Kynoar as adhesive Solution, LiNi as a positive electrode active material1/3Co1/3Mn1/3O2, the Li containing lithium iodide as solid electrolyte2S-P2S5 Series vitro-ceramic, and as conductive auxiliary agent VGCF (vapor phase method carbon fiber) be added polypropylene container in, with ultrasonic wavelength-division Set (エ ス エ ム テ ー system, trade name UH-50) in bulk is stirred 30 seconds.Thereafter, with oscillator (bavin field science Co. Ltd. system, ProductName TTM-1) polypropylene container is vibrated 3 minutes, then stirred 30 seconds with ultrasonic wave distributing device, make positive electrode active material Matter layer paste.
Using applicator, paste is used to be coated in as the aluminium foil of positive electrode collector positive electrode active material layer using scraper method On, it is 30 minutes dry on the hot plate for be heated to 100 DEG C thereafter, it is living with anode that lithium supply is thus made on positive electrode collector Property material layer.
(2) production of negative electrode active material layer
By the 5wt% butyl butyrate dissolved with the butyl butyrate as decentralized medium, the Kynoar as adhesive Solution, the Li containing lithium iodide as the silicon particle of negative electrode active material, as solid electrolyte2S-P2S5Series vitro-ceramic, And the VGCF (vapor phase method carbon fiber) as conductive auxiliary agent is added in polypropylene container, with ultrasonic wave distributing device stirring 30 Second.Thereafter, polypropylene container is vibrated 30 minutes with oscillator, production negative electrode active material layer paste.
Using applicator, paste is used to be coated in as the copper foil of negative electrode collector negative electrode active material layer using scraper method On, it is 30 minutes dry on the hot plate for be heated to 100 DEG C thereafter, negative electrode active material is thus made on negative electrode collector Layer.
(3) production of solid electrolyte layer
By the 5wt% n-heptane solution dissolved with the heptane as decentralized medium, the butadiene rubber as adhesive, and The Li containing lithium iodide as solid electrolyte2S-P2S5Series vitro-ceramic is added in polypropylene container, is dispersed with ultrasonic wave Device stirs 30 seconds.Thereafter, polypropylene container is vibrated 30 minutes with oscillator, production solid electrolyte layer paste.
The solid electrolyte layer of production paste is coated on aluminium foil using scraper method, is being heated to 100 DEG C thereafter It is 30 minutes dry on hot plate, thus make solid electrolyte layer.By lithium supply positive electrode active material layer, without inactivation lithium In the state that negative electrode active material layer has been overlapped with solid electrolyte layer respectively, with 6 tons/cm2It is suppressed, removes solid electrolytic Thus the Al foil of matter layer side makes the laminated body that positive electrode active material layer and solid electrolyte layer are used in lithium supply, and without mistake The negative electrode active material layer of lithium living and the laminated body of solid electrolyte layer.
(4) production of false all-solid lithium secondary battery
Respectively with the stamping tool of diameter 12.5mm to the layer of lithium supply positive electrode active material layer and solid electrolyte layer Stack carries out punching press, is rushed with laminated body of the tool of diameter 13.0mm to negative electrode active material layer and solid electrolyte layer Pressure.Both sides are laminated so that respective solid electrolyte layer adjoins one another, using constraint fixture with the confining pressure progress of 2N/m Constraint, has made false all-solid lithium secondary solid battery.
2. the charge and discharge pair false all-solid lithium secondary battery
False all-solid lithium secondary battery is put into drier, constant current-constant voltage is carried out with 0.05C and charges to 4.55V (terminating electric current 0.01C).Thereafter, 2.50V is discharged to constant current-constant voltage.Lithium is supplied to negative electrode active material as a result, Layer.
3. the decomposition of battery and reconstructing
Thereafter, the constraint for removing false all-solid lithium secondary battery is decomposed into lithium supply positive electrode active material layer and solid The laminated body of the laminated body of electrolyte layer and negative electrode active material layer and solid electrolyte layer without inactivation lithium.Cathode is living The laminated body of property material layer and solid electrolyte layer is referred to as the 1st laminated body.In addition, in addition to being used in false all-solid lithium secondary battery Lithium supply positive electrode active material layer lithium content become new production laminated body positive electrode active material layer lithium content 1.5 times, made by manufacturing method same as the laminated body of solid electrolyte layer as above-mentioned positive electrode active material layer New laminated body.Punching press is carried out to the new laminated body with the stamping tool of diameter 12.5mm, and calls it as the 2nd laminated body.
The engagement made by following methods is laminated on the 1st laminated body with solid electrolyte layer, so that the 1st laminated body Solid electrolyte layer be in contact with engagement with solid electrolyte layer, with 1.0 tons/cm2It is suppressed, removes the aluminium as substrate Foil.Thereafter, the 2nd laminated body is laminated, so that the solid electrolyte layer of the 2nd laminated body connects with engagement solid electrolyte layer Touching, with 6.0 tons/cm2It is suppressed, has made the all-solid lithium secondary battery of embodiment 8.
4. the production that solid electrolyte layer is used in engagement
By the 5wt% n-heptane solution dissolved with the heptane as decentralized medium, the butadiene rubber as adhesive, and The Li containing lithium iodide as solid electrolyte2S-P2S5Series vitro-ceramic is added in polypropylene container, is dispersed with ultrasonic wave Device stirs 30 seconds.Thereafter, polypropylene container is vibrated 30 minutes with oscillator, production engagement is used with solid electrolyte layer Paste.
It uses solid electrolyte layer that paste is used to be coated in as on the aluminium foil of substrate engagement using scraper method, is heating thereafter It is 30 minutes dry on to 100 DEG C of hot plates, engagement solid electrolyte layer is thus made on substrate, with the work of diameter 13.0mm Tool carries out punching press.
5. initial charge/discharge
The all-solid lithium secondary battery of the embodiment 8 of completion is put into drier, constant current-constant voltage is carried out with 0.05C Charge to 4.55V (terminating electric current 0.01C).Thereafter, 2.50V is discharged to constant current-constant voltage and measures its discharge capacity.
6. the measurement of capacity maintenance rate
After initial charge/discharge, the all-solid lithium secondary battery of embodiment 8 is charged to by constant current-constant voltage 4.40V is discharged to 2.50V by constant current-constant voltage, measures its discharge capacity (the 1st discharge capacity).Thereafter, 300 are repeated Secondary circulation following process: after charging to 4.17V with 0.5 hour rate (2C), it is discharged to 3.17V.After 300 circulations, pass through perseverance The all-solid lithium secondary battery of embodiment 8 is charged to 4.40V by electric current-constant voltage, passes through constant current-constant voltage discharge mode It is discharged to 2.50V and measures its discharge capacity (the 2nd discharge capacity).The 2nd discharge capacity/the 1st discharge capacity is calculated, capacity is measured Sustainment rate.
The > of < embodiment 9 and 10
So that layer of the lithium content of positive electrode active material layer used in false all-solid lithium secondary battery relative to new production The lithium content of the positive electrode active material layer of stack in embodiment 9 for 1.50 times, be 1.01 times in embodiment 10, except this with Outside, it operates similarly to Example 8, has made all-solid lithium secondary battery.
For the all-solid lithium secondary battery of embodiment 9 and 10, operation carries out initial charge/discharge similarly to Example 8, Measure discharge capacity.In addition, operation carries out similarly to Example 8 for the all-solid lithium secondary battery of embodiment 9 and 10 The measurement of capacity maintenance rate.
11 > of < embodiment
In the laminated body of positive electrode active material layer and solid electrolyte layer with negative electrode active material layer and solid electrolyte layer Laminated body between be inserted through and operate in the same way and the engagement solid electrolyte layer that makes and carry out with the method for embodiment 8 Stacking, in addition to this, the all-solid lithium for operating in the same way to obtain embodiment 11 with the all-solid lithium secondary battery of embodiment 8 is secondary Battery.For the all-solid lithium secondary battery of embodiment 11, operation carries out initial charge/discharge similarly to Example 8, and measurement is put Capacitance.In addition, operation carries out capacity maintenance rate similarly to Example 8 for the all-solid lithium secondary battery of embodiment 11 Measurement.
< measurement result >
Table 4 shows the manufacturing conditions of the all-solid-state battery of embodiment 8-11, battery composition and measurement result.
[table 4]
1. the explanation of table 4
In table 4, the presence or absence of " decomposition reconstruct " indicates to decompose all-solid-state battery and replace positive electrode active material layer The presence or absence of process (above-mentioned 3 " decomposition of battery and reconstruct ").
In table 4, " A " is the capacity that positive electrode active material layer is used in lithium supply, and positive-active is used in actually expression lithium supply The lithium content that material layer can release.In addition, " B " is the capacity of positive electrode active material layer, positive electrode active material layer is actually indicated The lithium content that can be released.Therefore, " A/B " is the capacity of lithium supply positive electrode active material layer divided by the appearance of positive electrode active material layer It is worth obtained from amount.It is explained, in embodiment 11, due to not carrying out above-mentioned 3 the decomposition of battery " and reconstruct ", because This does not have the record of numerical value.
In addition, " amorphous rate " and " Z/W " is as recording in the explanation of table 1.It is explained, for the sake of easy, in table 4 In, the specific value of " Z " and " W " is omitted.
" capacity maintenance rate " is that the result of the endurance test of the all-solid-state battery of embodiment 11 is set as to 100% and is calculated Value.In addition, " resistance " is the internal resistance of all-solid-state battery, it is to be set as the internal resistance of the all-solid-state battery of embodiment 11 100% and calculate value.
2. investigating
" resistance " of the all-solid lithium secondary battery of embodiment 10 is 96%, less than the secondary electricity of all-solid lithium of embodiment 11 " resistance " in pond.On the other hand, " capacity maintenance rate " of the all-solid lithium secondary battery of embodiment 10 is 132%, is greater than and implements " capacity maintenance rate " of the all-solid lithium secondary battery of example 11.
In the all-solid lithium secondary battery of embodiment 10, the lithium content that lithium supply can be released with positive electrode active material layer is i.e. The lithium content i.e. ratio of " B " that " A " and positive electrode active material layer can release is 1.01, although being not much different, with embodiment 11 Situation compare, resistance and capacity maintenance rate greatly improve.This is indicated, by by the bad because of charging of all-solid lithium secondary battery The positive electrode active material layer of change is substituted for new positive electrode active material layer, and can make reduces resistance and capacity maintenance rate improves All-solid lithium secondary battery.In addition, when compared with embodiment 8~10, it is believed that as the value of " A/B " increases, " resistance " subtracts Small and " capacity maintenance rate " improves.
It can thus be assumed that new by the way that the positive electrode active material layer deteriorated because having carried out initial charge process to be substituted for Positive electrode active material layer can be such that the cycle characteristics of all-solid-state battery further increases.
" relationship of initial charge amount and amorphous rate "
Following ratio be can be used as to calculate the amorphous rate, that is, assigned voltage is applied to carry out to all-solid-state battery After charged and discharged to 2.50V, in negative electrode active material layer, for the position using 5 μm away from solid electrolyte layer~15 μm TEM measurement and the visual field of 10 μm of 10 μ m that determines present in more than at least four particle silicon particle (comprising a part Silicon particle is not necessarily required to all images it can be seen that silicon particle), calculate the face of the decrystallized part of silicon particle Ratio of the product relative to the area for the silicon particle confirmed by BF image, using the ratio as amorphous rate.For embodiment 1, The all-solid-state battery of comparative example 1 and comparative example 2 has studied value and initial charge amount by the amorphous rate being calculated The relationship of value.
It is shown in table 5 the initial charge amount and amorphous rate of the all-solid-state battery of embodiment 1, comparative example 1 and comparative example 2 Relationship.
[table 5]
Initial charge amount (mAh/g) Amorphous rate (%)
Embodiment 1 896 30.4
Comparative example 1 858 26.5
Comparative example 2 770 21.0
It can be confirmed by the value of " the initial charge amount " and " amorphous rate " of embodiment 1, comparative example 1 and comparative example 2, such as Fig. 5 It is shown such, meet the relationship of " amorphous rate (%)=0.031 × initial charge amount (mAh) ".

Claims (9)

1. the manufacturing method of all-solid-state battery system, which has with positive electrode active material layer, solid electricity Charging/discharging voltage when solving the all-solid-state battery of matter layer and negative electrode active material layer and using the all-solid-state battery carries out The control device of control, the method comprising: being born by the positive electrode active material layer, the solid electrolyte layer and with alloy system The lamination process of the negative electrode active material layer stacking of pole active material particle, and the all-solid-state battery is charged to and is higher than The initial charge process of the initial charge voltage of the charging/discharging voltage.
2. method described in claim 1, wherein the alloy system negative electrode active material particle is silicon particle.
3. method of any of claims 1 or 2, wherein the charging/discharging voltage in the range of 2.50V or more 4.40V or less, And in the initial charge process, the initial charge voltage is greater than 4.45V and 5.00V or less.
4. method of any of claims 1 or 2, wherein the positive electrode active material layer has the anode for being coated with protective coating Active material, the protective coating are the metal oxide containing lithium.
5. method as claimed in claim 3, wherein the positive electrode active material layer has the positive-active for being coated with protective coating Substance, the protective coating are the metal oxide containing lithium.
6. method as claimed in claim 4, wherein the metal oxide containing lithium of protective coating is lithium niobate.
7. method described in claim 5, wherein the metal oxide containing lithium of protective coating is lithium niobate.
8. method as claimed in claim 4, wherein carry out the initial charge process in a manner of meeting following conditions:
(change rate dQ/dV of the charge volume Q to the voltage V in upper limit charging voltage in initial charge process)/(charging voltage is The average value of charge volume Q when 4.00V or more 4.40V or less to the change rate dQ/dV of voltage V) > 1.3.
9. method described in any one of claim 5~7, wherein carry out described initially filling in a manner of meeting following conditions Electrician's sequence:
(change rate dQ/dV of the charge volume Q to the voltage V in upper limit charging voltage in initial charge process)/(charging voltage is The average value of charge volume Q when 4.00V or more 4.40V or less to the change rate dQ/dV of voltage V) > 1.3.
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