CN106159318A - Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof - Google Patents
Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof Download PDFInfo
- Publication number
- CN106159318A CN106159318A CN201510161598.7A CN201510161598A CN106159318A CN 106159318 A CN106159318 A CN 106159318A CN 201510161598 A CN201510161598 A CN 201510161598A CN 106159318 A CN106159318 A CN 106159318A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solid
- lithium battery
- solid electrolyte
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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 Novel slice type solid-state serondary lithium battery of a kind of garnet-type solid electrolyte support and preparation method thereof, in described solid-state serondary lithium battery, positive pole is coated in the side of solid electrolyte, positive pole composition includes positive electrode active materials, polymer, lithium ion conductor and conductive carbon, wherein, positive electrode active materials includes LiFePO4、LiCoO2、LiMn2O4、LiNi0.5Mn1.5O4、LiNixCoyMn1-x-yO2And/or Li [LixM1-x]O2, M is at least one in Ni, Co, Mn, and polymer includes that at least one in PEO, PVdF, PMMA, PAN, lithium ion conductor include lithium salts, positive electrode active materials: conductive carbon: polymer: the mass ratio of lithium ion conductor is 10: 2: 1: z, z≤10.
Description
Technical field
The present invention relates to the chip solid-state serondary lithium battery that a kind of garnet-type solid electrolyte supports, belong to battery technology neck
Territory.
Background technology
Recently as the development of electric automobile and electrical network energy storage and the development of small-sized energy storage demand, exploitation can be in wide temperature
Use in the range of degree, there is high security, high-energy-density, power density and long-life battery the most necessary.Existing
Lithium ion battery uses organic liquid electrolytes, has the problems such as inflammable, electrochemical window is relatively low, it is impossible to meet following battery high
Than energy, the double requirements of high security.Solid lithium battery uses the inorganic solid electrolyte of pure solid-state or polymer dielectric to take
For organic liquid electrolytes, there is more preferable safety and heat stability, the most higher electrochemical window, it is possible to be suitable for high electricity
Pressure positive electrode, the most potential exploitation has the battery of high voltage, long-life, high security, at portable electric appts, electricity
The equipment such as motor-car and large-scale energy storage all has fabulous development prospect.
Garnet-type solid electrolyte Li7-xLa3Zr2-xTxO12(x=0-1, T=Al, Ta, Nb, W, Ga, Y, Te
Deng) it is the oxide inorganic solid electrolyte of a kind of good combination property, there is high conductivity at room temperature (up to 10-3
More than S/cm), wide electrochemical window (6V vs Li/Li+), good heat stability, stable to metal Li, in atmosphere can
Many advantages steady in a long-term and compatible with most of oxide anodes, therefore develops based on LLZTO oxide inorganic solid
The all-solid-state battery of electrolyte receives much concern.But the all-solid-state battery of oxide inorganic solid electrolyte exploitation unlike sulfide without
Machine solid electrolyte and polymer dielectric are smooth, and reason is as follows: oxide conductivity at room temperature is generally low than sulfide
An order of magnitude, simultaneous oxidation thing needs at high temperature to sinter and forms high fine and close ceramiic solid electrolyte, and high temperature exists lithium and waves
Send out, nonstoichiometry ratio, ionic conductivity reduce problem.More it is difficult to commonly use oxide anode such as LiCoO2With
LiFePO4Granule and Li7-xLa3Zr2-xTxO12The anode composite of granule mixing how with Li7-xLa3Zr2-xTxO12Ceramic electrolyte
In conjunction with, form the close anode composite/solid electrolyte interface of similar sulfide, thus reduce charge transfer resistance.
At present, research worker use such as on solid oxide electrolyte use pulsed laser deposition, aerosol deposition,
Sol-gel method prepares electrode film；The electrode coated slurry such as silk screen printing；And by discharge plasma sintering technique, altogether burning
Electrode is formed solid lithium battery with electrolyte by technology.But hull cell finite capacity, the electrode coated slurry such as silk screen printing
Method interface impedance is bigger, and discharge plasma sintering technique, altogether burning technology need higher temperature (> 790 DEG C), it is impossible to ensure
Chemically stable between positive pole and electrolyte.On this basis, it is contemplated that polymer has good adhesive property, polymer is solid
Body electrolyte can also form good ion transmission channel at anode composite, it may be considered that develops a kind of novel hydridization entirely solid
State battery construction method: i.e. polymer composite anode/garnet-type solid electrolyte/negative pole, the method use has sintered
Garnet-type solid electrolyte, follow-up without high-temperature process, thus solve solid lithium battery based on solid oxide electrolyte
The difficult problem run into.The method combines garnet-type solid electrolyte and the respective advantage of polymer, makes up respective deficiency simultaneously,
The most potential exploitation high voltage, long-life, the solid lithium battery of high safety.But, prior art also not about above-mentioned newly
The report of type hydridization all-solid-state battery.
Summary of the invention
It is contemplated that overcome the performance deficiency of existing solid-state serondary lithium battery, the invention provides a kind of solid-state secondary lithium electricity
Pond and preparation method thereof.
The invention provides a kind of solid-state serondary lithium battery, in described solid-state serondary lithium battery, positive pole is coated in solid electricity
Solving the side of matter, positive pole composition includes positive electrode active materials, polymer, lithium ion conductor and conductive carbon, wherein, positive-active
Material includes LiFePO4、LiCoO2、LiMn2O4、LiNi0.5Mn1.5O4、LiNixCoyMn1-x-yO2And/or Li [LixM1- x]O2, M is at least one in Ni, Co, Mn, and polymer includes in PEO, PVdF, PMMA, PAN at least
One, lithium ion conductor includes lithium salts, positive electrode active materials: conductive carbon: polymer: the mass ratio of lithium ion conductor is
10:2:1:z, z≤10.
It is preferred that lithium ion conductor includes LiClO4、LiPF6、LiAsF6、LiBF4、LiCF3SO3、
LiN(CF3SO2)2、LiN(C2F5SO2)2、LiPF3(CF3CF2)3、LiBF3CF3CF2、LiC(CF3SO2)3、
LiB(C2O4)2、LiBF2(CO2)2, polymerization lithium borate salt PLTB, lithium lanthanum zirconium oxygen, Li-La-Ti oxygen, titanium phosphate aluminum lithium, silicon phosphorus
At least one in acid lithium.
It is preferred that conductive carbon includes acetylene black, graphite, Graphene, graphene oxide, porous carbon, CNT, carbon
At least one in fiber, nitrogen-doped carbon.
It is preferred that solid electrolyte is material is Li7-xLa3Zr2-xTxO12Potsherd, x=0-1, T are Al, Ta,
At least one in Nb, W, Ga, Y, Te, solid electrolyte thickness is 0.1 μm-10mm.
It is preferred that described solid-state serondary lithium battery also includes being coated in the negative pole of solid electrolyte opposite side, electrode current collecting
Body, encapsulating material, conduction lug and/or pole.
It is preferred that the composition of negative pole includes lithium, lithium alloy and/or the complex containing lithium metal, wherein, lithium in lithium alloy
Content is at least 20wt%, and lithium alloy is possibly together with in Mg, Ca, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb
At least one；
Complex containing lithium metal at least contains the lithium metal of 20wt%, also comprises carbon granule, CNT, carbon fiber, graphite
Alkene, graphite flake, porous metals, porous carbon, indifferent oxide and/or copper powder.
It is preferred that the material of plus plate current-collecting body includes rustless steel, Ni, Al and/or Ti.
It is preferred that the operating temperature of solid-state serondary lithium battery is room temperature to 150 DEG C, it is preferable that operating temperature is 60-100 DEG C.
Also, present invention also offers the preparation method of a kind of above-mentioned solid-state serondary lithium battery, including:
1) according to the composition of described positive pole, the preparation slurry containing positive pole composition；
2) by step 1) slurry prepared is coated on the side of solid electrolyte, then carries out being compacted, being dried so that and polymer is solid
Change；
3) opposite side at solid electrolyte prepares negative pole.
Beneficial effects of the present invention:
1, the anode composite that is not both that the present invention is maximum compared with other carbuncle type all-solid-state batteries uses the poly-of interpolation lithium ion conducting material
Compound transmission lithium ion, improves lithium ion conductance, and the adhesive property that polymer is excellent simultaneously guarantees that anode composite is solid with ceramic inorganic
Body electrolyte forms good affixed touch, and reduces interface resistance；
2, this hydridization is prepared scheme and be need not active material is carried out high-temperature process, simpler energy-conservation, maintains active material simultaneously
Structure, has good cycle performance and high rate performance, and after circulating 100 times under 1C multiplying power when 100 DEG C, capacity dimension holdup exists
More than 93%, coulombic efficiency is more than 99%；
3, this solid state battery can normally work from room temperature to 150 DEG C, solves liquid state batteries high temperature safe problem, in certain limit
In, temperature heals high electrochemical performance better, it is possible to meet the application of special occasions battery, such as electric motor car and space field；
4, use Garnet-type solid electrolyte as support, can directly use lithium metal as negative material, be remarkably improved battery
Energy density.
Accompanying drawing explanation
Fig. 1 is that the structural representation of all solid state serondary lithium battery in one embodiment of the present invention (is shown that this device in figure
The cross section of part all parts), wherein, 1-negative metal lithium, 2-carbuncle type ceramic electrolyte sheet, 3-positive active particles, 4-
Polymer, lithium salts and conductive carbon (3 and 4 constitute polymer composite anode), 5-stainless steel substrates, 6-encapsulating material；
Fig. 2 is Li in the present invention7-xLa3Zr2-xTaxO12(LLZTO) XRD figure (2a) of potsherd and room temperature ac impedance spectroscopy
(2b)；
Fig. 3 is that section SEM figure (3a) and surface SEM of all-solid-state battery in the embodiment of the present invention 2 scheme (3b)；
Fig. 4 be in the present invention 1# all-solid-state battery in 0.05C multiplying power, front 10 charging and discharging curves (4a) of 60 DEG C and the present invention
Middle 1# all-solid-state battery at 60 DEG C, front 50 cycle performances (4b) of 0.05C multiplying power；
Fig. 5 is 2# all-solid-state battery high rate performance at 60 DEG C in the present invention；
Fig. 6 be in the present invention 3# all-solid-state battery at 100 DEG C, front 100 cycle performances of 1C multiplying power；
Fig. 7 is 4# all-solid-state battery high rate performance under room temperature (25 DEG C) in the present invention.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment are only below in conjunction with accompanying drawing and following embodiment
For the present invention is described, and the unrestricted present invention.
Present invention aim at the high temperature for solid lithium battery based on garnet-type solid electrolyte structure exists to be stranded
The weak points such as difficulty, complex process, propose the hybridization embodiments using polymer composite anode to combine garnet-type solid electrolyte.
The invention provides the Novel slice type solid-state serondary lithium battery that a kind of garnet-type solid electrolyte supports, described complete solid
State serondary lithium battery includes: the ceramic sheet of carbuncle type lithium ion conductor is as the working electrolyte of battery, and as battery
Supporter；Negative pole, including lithium, lithium alloy or the complex containing lithium metal, forms good interface with the one side of potsherd and contacts；
Positive pole, is made by positive electrode active materials, polymer, lithium ion conductor and conductive carbon are compound, is formed good with the another side of potsherd
Good interracial contact；Electrode current collecting body, is made up of the tinsel stable with electrode material chemistry and electrochemical contact.
Preferably, in lithium alloy, in lithium alloy, the content of lithium is at least 20wt%, lithium alloy possibly together with Mg, Ca, B,
One or more in Al, Ga, In, Si, Ge, Sn, Pb, Sb；Complex containing lithium metal, at least contains 20wt%
Lithium metal, also comprise carbon granule, CNT, carbon fiber, Graphene, graphite flake, porous metals, porous carbon, inertia
Oxide and/or copper powder.
Preferably, described garnet-type solid electrolyte is Li7-xLa3Zr2-xTxO12(x=0-1, T=Al, Ta, Nb,
W, Ga, Y, Te etc.) potsherd, thickness is 0.1 μm-10mm.
Preferably, in polymer combination electrode, polymer can be PEO, PVdF, PMMA, PAN and its copolymerization
One or both in thing are blended.
Preferably, in polymer combination electrode, lithium ion conductor can be lithium salts LiClO4、LiPF6、LiAsF6、
LiBF4、LiCF3SO3、LiN(CF3SO2)2(LiTFSI)、LiN(C2F5SO2)2(LiBETI)、LiPF3(CF3CF2)3
(LiFAP)、LiBF3CF3CF2(LiFAB)、LiC(CF3SO2)3(LiTFSM)、LiB(C2O4)2(LiBOB)、
LiBF2(CO2)2(LiODFB), one or more in polymerization lithium borate salt PLTB, it is also possible to be lithium lanthanum zirconium oxygen, Li-La-Ti
One or more of the powder body materials such as oxygen, titanium phosphate aluminum lithium, silicon lithium phosphate.
Preferably, in polymer combination electrode, positive electrode active materials can be LiFePO4、LiCoO2、LiMn2O4、
LiNi0.5Mn1.5O4, ternary material LiNixCoyMn1-x-yO2Or lithium-rich manganese base material Li [LixM1-x]O2(M=Ni, Co,
Mn or combination in any).
Preferably, in polymer combination electrode, conductive materials carbon can be acetylene black, graphite, Graphene, graphite oxide
One or more in alkene, porous carbon, CNT, carbon fiber, nitrogen-doped carbon.
Preferably, plus plate current-collecting body can be rustless steel, Ni, Al, Ti paper tinsel or theirs is material modified.
Preferably, described solid lithium battery also includes encapsulating negative pole, solid-state electrolyte layer, the electricity of polymer composite anode
Pond encapsulating material, and can be at the conduction lug of operating temperature use, pole.
Preferably, the operating temperature of described all solid state serondary lithium battery be room temperature to 150 DEG C, preferably operating temperature be 60-100
℃。
Preferably, the preparation method of described solid lithium battery, it is characterised in that comprise the steps of
1) chemical formula Li is pressed7-xLa3Zr2-xTxO12Li in (x=0-1, T=Al, Ta, Nb, W, Ga, Y, Te etc.), La,
The mol ratio of Zr, T, chooses LiOH, La (OH)3、ZrO2With corresponding oxide TxOyMake raw material, wherein LiOH excess
5-20%, by its 10-30 hour post-drying of ball milling in ethanol medium, then calcines 6-10 hour at 850-1000 DEG C, obtains
Li7-xLa3Zr2-xTxO12Ceramics.Ceramics is transferred in carbon die, under an ar atmosphere, hot pressed sintering, 1000-1200
DEG C, 15MPa sinter 1-2 hour.It is subsequently processed into the potsherd of desired thickness and size；
2) appropriate lithium ion conductor and organic solvent addition mortar will make Lithium Ionic Conducting Materials fully dispersed in dry atmosphere
Or dissolve, then grind together with the addition of positive electrode active materials, conductive carbon material and polymer solution, be uniformly mixed answers
Close positive pole.Wherein positive electrode active materials: carbon: polymer: the mass ratio of lithium ion conductor is 10:2:1:z, z=0-10；
3) a certain amount of anode composite is coated to the one side of potsherd, natural cooling under room temperature, then dries in drying baker, use
Corrosion resistant plate is compacted, and is finally dried in vacuum drying oven, solidifies polymer while making organic solvent volatilize completely；
4) the potsherd another side of coating anode composite after the drying prepares metal lithium electrode and collector, then encapsulates, assembled
Without adding the electrolyte such as EC, PC in journey.
Beneficial effects of the present invention:
1, the anode composite that is not both that the present invention is maximum compared with other carbuncle type all-solid-state batteries uses the poly-of interpolation lithium ion conducting material
Compound transmission lithium ion, improves lithium ion conductance, and the adhesive property that polymer is excellent simultaneously guarantees that anode composite is solid with ceramic inorganic
Body electrolyte forms good affixed touch, and reduces interface resistance；
2, this hydridization is prepared scheme and be need not active material is carried out high-temperature process, simpler energy-conservation, maintains active material simultaneously
Structure, has good cycle performance and high rate performance, and after circulating 100 times under 1C multiplying power when 100 DEG C, capacity dimension holdup exists
More than 93%, coulombic efficiency is more than 99%；
3, this solid state battery can normally work from room temperature to 150 DEG C, solves liquid state batteries high temperature safe problem, in certain limit
In, temperature heals high electrochemical performance better, it is possible to meet the application of special occasions battery, such as electric motor car and space field；
4, use Garnet-type solid electrolyte as support, can directly use lithium metal as negative material, be remarkably improved battery
Energy density.
The invention provides all solid state serondary lithium battery of Novel slice type that a kind of garnet-type solid electrolyte supports.Its feature
It is that in the one side of pottery, coating is led by polymer, lithium ion using the ceramic sheet of garnet-type solid electrolyte as support
Body, conductive carbon and the anode composite of electrode material composition, form good interface between the two；At another side, deposit or suppress
Lithium, lithium alloy or the complex containing lithium metal are as negative pole.The advantage that anode composite is constituted is effectively to reduce electrode/electrolyte
Between while solid/liquid/solid interface resistance, improve the electric conductivity of positive pole.This solid state battery construction method Simple temperature and, it is not necessary to high
Temperature processes.With LiFePO4The battery constructed Deng common used material all shows excellent circulation and the most forthright at 25,60,100 DEG C
Energy.The constructed battery made of the present invention is on the premise of ensureing high-performance, and the safety that can effectively solve serondary lithium battery is asked
Topic is significant in the secondary cell of electric automobile and energy storage field for development and application.
The working mechanism of solid state battery of the present invention is:
Solid state battery does not add any organic solvent, in polymer combination electrode, and Li+Complex is formed, by poly-with polymer
Polymer segments moves repeatedly, Li+Constantly dissociate and complexation with polymer, move forward simultaneously, thus conduct Li+, high temperature helps
Moving in polymer segment, when therefore temperature improves within the specific limits, ionic conductivity is higher.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following example are served only for this
Bright it is further described, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art is according to the present invention's
Some nonessential improvement and adjustment that foregoing is made belong to protection scope of the present invention.The technique ginseng that following example is concrete
Number etc. is the most only an example in OK range, in the range of i.e. those skilled in the art can be done suitably by explanation herein
Select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
A kind of all solid state serondary lithium battery of novel hybride based on garnet-type solid electrolyte, the structure of device is shown in accompanying drawing 1, uses
Negative pole 1, solid electrolyte layer 2, polymer composite anode 3 and 4, specific as follows:
Solid electrolyte layer: use the Li of high-compactness7-xLa3Zr2-xTaxO12(LLZTO) potsherd (consistency is more than 96%),
Not only can transmit lithium ion but also can protect the dielectric substrate of lithium metal, thickness is 0.1 μm-10mm；
Polymer composite anode: in inert-atmosphere glove box, appropriate lithium salts and NMP are added in agate mortar and make lithium salts the most molten
Solve, then by LiFePO4, conductive carbon add in mortar, finally take the PVdF solution (solvent is NMP) prepared in advance and turn
Move on to mortar grinds with pestle, the anode composite being evenly distributed, wherein LiFePO4: the mass ratio of C:PVdF: lithium salts is
10:2:1:x, x=0-10.A certain amount of anode composite scraper is coated to the one side of potsherd, the coldest under room temperature
But, then dry in drying baker, be compacted with corrosion resistant plate, be finally dried in vacuum drying oven, make solvent NMP complete
Polymer is made to solidify while volatilization；
Negative pole: be placed in inert-atmosphere glove box by the potsherd of coated polymer anode composite, is then pressed in pottery by negative metal lithium sheet
The another side of porcelain electrolyte sheet, then uses the battery being assembled into described in Fig. 1.Then by this battery room temperature (25 DEG C), 60
DEG C, test at 100 DEG C.
Embodiment 2
A kind of all solid state serondary lithium battery of novel hybride based on garnet-type solid electrolyte, the structure of device is same as in Example 1.
The preparation method of solid electrolyte layer reaches 99% with embodiment 1, the relative density of LLZTO potsherd, its XRD such as Fig. 2 a
Shown in, it is seen that ceramic major is cubic garnet structure.The circular Li electrode of employing is as test electrode, at room temperature to pottery
Sample carries out electric performance test, obtains shown in its ac impedance spectroscopy 2b, and calculating conductivity at room temperature is 6.6 × 10-4S·cm- 1。
Embodiment 3
A kind of all solid state serondary lithium battery of novel hybride based on garnet-type solid electrolyte, the structure of device is same as in Example 1,
The negative pole 1, solid electrolyte layer 2, polymer composite anode 3 and 4 that use and specific as follows:
The solid electrolyte layer used is with embodiment 1,2；
Negative pole preparation process is with embodiment 1；
Polymer composite anode LiFePO4: the mass ratio of C:PVdF: lithium salts is 10:2:1:5 (1# solid state battery)；
Battery testing temperature: 60 DEG C；
As shown in Figure 3 a, Fig. 3 b is that the back of the body of anode composite surface SEM dissipates to the section SEM secondary electron image of anode composite/LLZTO
Penetrate charge pattern.Fig. 4 a be 1# solid state battery at 60 DEG C, front 10 charging and discharging curves under 0.05C multiplying power, Fig. 4 b is 1# solid-state
Battery at 60 DEG C, front 50 cyclic curves under 0.05C multiplying power.
Embodiment 4
A kind of all solid state serondary lithium battery of novel hybride based on garnet-type solid electrolyte, the structure of device is same as in Example 1,
The negative pole 1 of employing, solid electrolyte layer 2, polymer composite anode 3 and 4, specific as follows:
The solid electrolyte layer used is with example 1,2,3；
Negative pole preparation process is with embodiment 1,3；
Polymer composite anode LiFePO4: the mass ratio of C:PVdF: lithium salts is 10:2:1:7.5 (2# solid state battery)；
Battery testing temperature: 60 DEG C；
Fig. 5 shows 2# solid state battery high rate performance of 0.05C, 0.1C, 0.2C, 0.5C and 1C electric current when 60 DEG C.
Embodiment 5
A kind of all solid state serondary lithium battery of novel hybride based on garnet-type solid electrolyte, the structure of device is same as in Example 1,
The negative pole 1 of employing, solid electrolyte layer 2, polymer composite anode 3 and 4, specific as follows:
The solid electrolyte layer used is with embodiment 1,2,3,4；
Negative pole preparation process is with example 1,3,4；
Polymer composite anode LiFePO4: the mass ratio of C:PVdF: lithium salts is 10:2:1:7.5, with embodiment 4；
Battery testing temperature: 100 DEG C (3# solid state battery)；
Fig. 6 show 3# solid state battery at 100 DEG C, the cycle performance that 1C is first 100 times.
Embodiment 6
A kind of all solid state serondary lithium battery of novel hybride based on garnet-type solid electrolyte, the structure of device is same as in Example 1,
The negative pole 1 of employing, solid electrolyte layer 2, polymer composite anode 3 and 4, specific as follows:
The solid electrolyte layer used is with embodiment 1,2,3,4,5；
Negative pole preparation process is with embodiment 1,3,4,5；
Polymer composite anode LiFePO4: the mass ratio of C:PVdF: lithium salts is 10:2:1:7.5, with example 4,5；
Battery testing temperature: 25 DEG C (4# solid state battery)；
Fig. 7 shows the 4# solid state battery high rate performance at room temperature (25 DEG C) 0.05C, 0.1C, 0.2C, 0.5C.
The present invention has a following significant advantage:
(1) production method is gentle simple
Traditional solid state battery based on garnet-type solid electrolyte needs electrode and electrolyte are carried out high temperature sintering, is easily caused electricity
Pole and/or electrolyte reaction, complex process simultaneously.This hybridization embodiments uses the ceramiic solid electrolyte prepared, as long as
The electrode slurry technology of preparing and the coating processes that use routine can obtain ceramic base all-solid-state battery prototype.Without to compound electric
Pole carries out high-temperature process, maintains the performance of active material；
(2) long circulation life
This solid state battery is at 60 and 100 DEG C respectively with the current charge-discharge electricity of 0.05C and 1C, and after circulating 100 times, capability retention exists
More than 93%, coulombic efficiency is more than 99%；
(3) high security
This solid state battery is not added with any organic solvent, there will not be any danger at 100 DEG C of high temperature.Additionally LLZTO solid electrolytic
Matter itself has high thermal stability, high corrosion resistance and electrochemical window, substantially increases the safety in system work process
Can, the electrochemical window of solid state battery can be improved simultaneously, be suitable for high-voltage anode material；
(4) wider use temperature range
This solid state battery room temperature (25 DEG C), 60 DEG C, 100 DEG C all there is good chemical property, simultaneously because polymer lithium salts with
And ceramiic solid electrolyte all improves along with temperature both elevated ionic electrical conductivity, the impedance of whole battery significantly reduces at 100 DEG C, reaches
To liquid state batteries level, there is large current density power, it is contemplated that battery performance will further improve at a higher temperature, especially
It is suitable for there is temperature controlled application.
Claims (9)
1. a solid-state serondary lithium battery, it is characterised in that in described solid-state serondary lithium battery, positive pole is coated in the side of solid electrolyte, positive pole composition includes positive electrode active materials, polymer, lithium ion conductor and conductive carbon, and wherein, positive electrode active materials includes LiFePO4、LiCoO2、LiMn2O4、LiNi0.5Mn1.5O4、LiNixCoyMn1-x-yO2And/or Li [LixM1-x]O2, M is at least one in Ni, Co, Mn, and polymer includes that at least one in PEO, PVdF, PMMA, PAN, lithium ion conductor include lithium salts, positive electrode active materials: conductive carbon: polymer: the mass ratio of lithium ion conductor is 10:2:1:z, z≤10.
Solid-state serondary lithium battery the most according to claim 1, it is characterised in that lithium ion conductor includes LiClO4、LiPF6、LiAsF6、LiBF4、LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiPF3(CF3CF2)3、LiBF3CF3CF2、LiC(CF3SO2)3、LiB(C2O4)2、LiBF2(CO2)2, polymerization lithium borate salt PLTB, lithium lanthanum zirconium oxygen, Li-La-Ti oxygen, titanium phosphate aluminum lithium, silicon lithium phosphate at least one.
Solid-state serondary lithium battery the most according to claim 1 and 2, it is characterised in that conductive carbon includes at least one in acetylene black, graphite, Graphene, graphene oxide, porous carbon, CNT, carbon fiber, nitrogen-doped carbon.
4. according to described solid-state serondary lithium battery arbitrary in claim 1-3, it is characterised in that solid electrolyte be material be Li7-xLa3Zr2-xTxO12Potsherd, x=0-1, T are at least one in Al, Ta, Nb, W, Ga, Y, Te, and solid electrolyte thickness is 0.1 μm-10 mm.
5. according to described solid-state serondary lithium battery arbitrary in claim 1-4, it is characterised in that described solid-state serondary lithium battery also includes being coated in the negative pole of solid electrolyte opposite side, electrode current collecting body, encapsulating material, conduction lug and/or pole.
6. according to described solid-state serondary lithium battery arbitrary in claim 1-5, it is characterized in that, the composition of negative pole includes lithium, lithium alloy and/or the complex containing lithium metal, wherein, in lithium alloy, the content of lithium is at least 20 wt%, and lithium alloy is possibly together with at least one in Mg, Ca, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb；
Complex containing lithium metal at least contains 20
The lithium metal of wt%, also comprises carbon granule, CNT, carbon fiber, Graphene, graphite flake, porous metals, porous carbon, indifferent oxide and/or copper powder.
7. according to described solid-state serondary lithium battery arbitrary in claim 1-6, it is characterised in that the material of plus plate current-collecting body includes rustless steel, Ni, Al and/or Ti.
8. according to described solid-state serondary lithium battery arbitrary in claim 1-7, it is characterised in that the operating temperature of solid-state serondary lithium battery is room temperature to 150 DEG C, it is preferable that operating temperature is 60-100 DEG C.
9. the preparation method of arbitrary described solid-state serondary lithium battery in claim 1-8, it is characterised in that including:
1) according to the composition of described positive pole, the preparation slurry containing positive pole composition；
2) slurry prepared by step 1) is coated on the side of solid electrolyte, then carries out being compacted, being dried so that polymer solidifies；
3) opposite side at solid electrolyte prepares negative pole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510161598.7A CN106159318A (en) | 2015-04-07 | 2015-04-07 | Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510161598.7A CN106159318A (en) | 2015-04-07 | 2015-04-07 | Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106159318A true CN106159318A (en) | 2016-11-23 |
Family
ID=57337650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510161598.7A Pending CN106159318A (en) | 2015-04-07 | 2015-04-07 | Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106159318A (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107017388A (en) * | 2017-02-09 | 2017-08-04 | 上海蔚来汽车有限公司 | A kind of preparation method of composite positive pole for solid lithium ion battery |
| CN107565090A (en) * | 2017-08-30 | 2018-01-09 | 清陶（昆山）能源发展有限公司 | A kind of positive plate of lithium battery and preparation method thereof |
| CN107579276A (en) * | 2017-07-25 | 2018-01-12 | 华南理工大学 | A kind of solid polymer electrolyte membrane and preparation method thereof and the application as lithium ion battery barrier film |
| CN107591568A (en) * | 2017-08-19 | 2018-01-16 | 电子科技大学 | A kind of preparation method of stacked all-solid lithium-ion battery |
| CN107591536A (en) * | 2017-09-02 | 2018-01-16 | 清陶（昆山）能源发展有限公司 | Gel anode composite piece and preparation method thereof and the method for preparing solid lithium battery |
| CN107706352A (en) * | 2017-10-13 | 2018-02-16 | 清陶（昆山）能源发展有限公司 | A kind of anode pole piece applied to flexible solid lithium battery and preparation method thereof |
| CN108365165A (en) * | 2018-02-06 | 2018-08-03 | 哈尔滨工业大学 | A kind of solid state lithium battery and preparation method thereof of novel electrolytes complex method |
| CN108539182A (en) * | 2018-05-14 | 2018-09-14 | 哈尔滨工业大学 | A kind of preparation method of composite sulfur positive electrode and its application in all solid state lithium-sulfur cell |
| CN108598561A (en) * | 2018-03-08 | 2018-09-28 | 浙江大学 | A kind of quasi- solid lithium ion conducting electrolyte and its preparation method and application |
| CN108923060A (en) * | 2018-06-29 | 2018-11-30 | 桑顿新能源科技有限公司 | A kind of solid state lithium battery and preparation method of modifying interface |
| CN109119684A (en) * | 2017-06-22 | 2019-01-01 | 精工爱普生株式会社 | Electrolyte, battery and electronic equipment |
| CN109360947A (en) * | 2018-08-31 | 2019-02-19 | 哈尔滨理工大学 | A kind of preparation method of the porous carbon positive electrode of quasi- solid-state lithium-sulfur cell |
| CN109742332A (en) * | 2018-11-23 | 2019-05-10 | 颍上北方动力新能源有限公司 | A kind of production method of positive plate of lithium battery |
| CN110224120A (en) * | 2019-05-23 | 2019-09-10 | 清华大学深圳研究生院 | Preparation method, combination electrode and the lithium ion battery of combination electrode |
| CN110395980A (en) * | 2019-07-26 | 2019-11-01 | 惠州市富济电子材料有限公司 | Porous ceramic film material, solid electrolyte material and preparation method thereof and lithium ion battery |
| CN110447127A (en) * | 2017-03-20 | 2019-11-12 | 罗伯特·博世有限公司 | Electrode active material, the method for preparing the electrode active material and the Anode and battery comprising the electrode active material |
| CN110832687A (en) * | 2018-03-27 | 2020-02-21 | 株式会社Lg化学 | Composite solid electrolyte membrane for all-solid battery and all-solid battery comprising same |
| CN111106392A (en) * | 2019-12-30 | 2020-05-05 | 华南师范大学 | Preparation method of all-solid-state electrolyte battery |
| CN111755733A (en) * | 2019-03-28 | 2020-10-09 | 揖斐电株式会社 | All-solid-state battery and method for manufacturing same |
| CN111868994A (en) * | 2017-11-07 | 2020-10-30 | 密执安州立大学董事会 | Solid-state battery electrolyte with improved stability to cathode materials |
| CN111886090A (en) * | 2018-02-15 | 2020-11-03 | 马里兰大学派克分院 | Ordered porous solid electrolyte structure, electrochemical device having the same, and method of manufacturing the same |
| CN112514136A (en) * | 2018-03-08 | 2021-03-16 | 崔屹 | Solid electrolyte based molten lithium electrochemical cell |
| CN114335758A (en) * | 2021-12-31 | 2022-04-12 | 郑州大学 | Garnet solid electrolyte based high-temperature molten lithium iodine battery |
| CN114551985A (en) * | 2021-07-27 | 2022-05-27 | 万向一二三股份公司 | High-toughness high-conductivity inorganic solid composite electrolyte and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067529A (en) * | 1991-06-04 | 1992-12-30 | 中国科学院物理研究所 | Mix all solid state room temperature lithium storage battery of phase solid electrolyte and preparation method thereof |
| US20040130061A1 (en) * | 2002-03-07 | 2004-07-08 | Paul-Andre Lavoie | Positive electrode films for alkali metal polymer batteries and method for making same |
| CN103113107A (en) * | 2013-02-28 | 2013-05-22 | 中国科学院上海硅酸盐研究所 | Method for preparing ceramic solid electrolyte |
-
2015
- 2015-04-07 CN CN201510161598.7A patent/CN106159318A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067529A (en) * | 1991-06-04 | 1992-12-30 | 中国科学院物理研究所 | Mix all solid state room temperature lithium storage battery of phase solid electrolyte and preparation method thereof |
| US20040130061A1 (en) * | 2002-03-07 | 2004-07-08 | Paul-Andre Lavoie | Positive electrode films for alkali metal polymer batteries and method for making same |
| CN103113107A (en) * | 2013-02-28 | 2013-05-22 | 中国科学院上海硅酸盐研究所 | Method for preparing ceramic solid electrolyte |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107017388A (en) * | 2017-02-09 | 2017-08-04 | 上海蔚来汽车有限公司 | A kind of preparation method of composite positive pole for solid lithium ion battery |
| CN110447127A (en) * | 2017-03-20 | 2019-11-12 | 罗伯特·博世有限公司 | Electrode active material, the method for preparing the electrode active material and the Anode and battery comprising the electrode active material |
| CN109119684B (en) * | 2017-06-22 | 2023-02-28 | 精工爱普生株式会社 | Electrolyte, battery, and electronic device |
| CN109119684A (en) * | 2017-06-22 | 2019-01-01 | 精工爱普生株式会社 | Electrolyte, battery and electronic equipment |
| CN107579276A (en) * | 2017-07-25 | 2018-01-12 | 华南理工大学 | A kind of solid polymer electrolyte membrane and preparation method thereof and the application as lithium ion battery barrier film |
| CN107591568A (en) * | 2017-08-19 | 2018-01-16 | 电子科技大学 | A kind of preparation method of stacked all-solid lithium-ion battery |
| CN107591568B (en) * | 2017-08-19 | 2019-12-10 | 电子科技大学 | Preparation method of laminated all-solid-state lithium ion battery |
| CN107565090A (en) * | 2017-08-30 | 2018-01-09 | 清陶（昆山）能源发展有限公司 | A kind of positive plate of lithium battery and preparation method thereof |
| CN107591536B (en) * | 2017-09-02 | 2020-08-11 | 清陶（昆山）能源发展有限公司 | Gel composite positive plate, preparation method thereof and method for preparing all-solid-state lithium battery |
| CN107591536A (en) * | 2017-09-02 | 2018-01-16 | 清陶（昆山）能源发展有限公司 | Gel anode composite piece and preparation method thereof and the method for preparing solid lithium battery |
| CN107706352B (en) * | 2017-10-13 | 2020-09-04 | 清陶（昆山）能源发展有限公司 | Positive pole piece applied to flexible solid-state lithium battery and preparation method thereof |
| CN107706352A (en) * | 2017-10-13 | 2018-02-16 | 清陶（昆山）能源发展有限公司 | A kind of anode pole piece applied to flexible solid lithium battery and preparation method thereof |
| CN111868994A (en) * | 2017-11-07 | 2020-10-30 | 密执安州立大学董事会 | Solid-state battery electrolyte with improved stability to cathode materials |
| CN108365165A (en) * | 2018-02-06 | 2018-08-03 | 哈尔滨工业大学 | A kind of solid state lithium battery and preparation method thereof of novel electrolytes complex method |
| CN108365165B (en) * | 2018-02-06 | 2020-05-19 | 哈尔滨工业大学 | Solid-state lithium battery with novel electrolyte composite mode and preparation method thereof |
| CN111886090B (en) * | 2018-02-15 | 2023-07-04 | 马里兰大学派克分院 | Ordered porous solid electrolyte structure, electrochemical device having the same, and method of manufacturing the same |
| CN111886090A (en) * | 2018-02-15 | 2020-11-03 | 马里兰大学派克分院 | Ordered porous solid electrolyte structure, electrochemical device having the same, and method of manufacturing the same |
| CN108598561A (en) * | 2018-03-08 | 2018-09-28 | 浙江大学 | A kind of quasi- solid lithium ion conducting electrolyte and its preparation method and application |
| CN112514136A (en) * | 2018-03-08 | 2021-03-16 | 崔屹 | Solid electrolyte based molten lithium electrochemical cell |
| US11476498B2 (en) | 2018-03-27 | 2022-10-18 | Lg Energy Solution, Ltd. | Complex solid electrolyte membrane for all-solid-state battery and all-solid-state battery including same |
| CN110832687B (en) * | 2018-03-27 | 2023-05-05 | 株式会社Lg新能源 | Composite solid electrolyte membrane for all-solid battery and all-solid battery comprising same |
| CN110832687A (en) * | 2018-03-27 | 2020-02-21 | 株式会社Lg化学 | Composite solid electrolyte membrane for all-solid battery and all-solid battery comprising same |
| CN108539182B (en) * | 2018-05-14 | 2020-07-17 | 哈尔滨工业大学 | Preparation method of composite sulfur positive electrode material and application of composite sulfur positive electrode material in all-solid-state lithium-sulfur battery |
| CN108539182A (en) * | 2018-05-14 | 2018-09-14 | 哈尔滨工业大学 | A kind of preparation method of composite sulfur positive electrode and its application in all solid state lithium-sulfur cell |
| CN108923060A (en) * | 2018-06-29 | 2018-11-30 | 桑顿新能源科技有限公司 | A kind of solid state lithium battery and preparation method of modifying interface |
| CN109360947B (en) * | 2018-08-31 | 2022-01-28 | 哈尔滨理工大学 | Preparation method of porous carbon cathode material of quasi-solid-state lithium-sulfur battery |
| CN109360947A (en) * | 2018-08-31 | 2019-02-19 | 哈尔滨理工大学 | A kind of preparation method of the porous carbon positive electrode of quasi- solid-state lithium-sulfur cell |
| CN109742332A (en) * | 2018-11-23 | 2019-05-10 | 颍上北方动力新能源有限公司 | A kind of production method of positive plate of lithium battery |
| CN111755733A (en) * | 2019-03-28 | 2020-10-09 | 揖斐电株式会社 | All-solid-state battery and method for manufacturing same |
| CN110224120A (en) * | 2019-05-23 | 2019-09-10 | 清华大学深圳研究生院 | Preparation method, combination electrode and the lithium ion battery of combination electrode |
| CN110395980B (en) * | 2019-07-26 | 2022-02-11 | 深圳市富济新材料科技有限公司 | Porous ceramic material, solid electrolyte material, preparation method of solid electrolyte material and lithium ion battery |
| CN110395980A (en) * | 2019-07-26 | 2019-11-01 | 惠州市富济电子材料有限公司 | Porous ceramic film material, solid electrolyte material and preparation method thereof and lithium ion battery |
| CN111106392A (en) * | 2019-12-30 | 2020-05-05 | 华南师范大学 | Preparation method of all-solid-state electrolyte battery |
| CN114551985A (en) * | 2021-07-27 | 2022-05-27 | 万向一二三股份公司 | High-toughness high-conductivity inorganic solid composite electrolyte and preparation method thereof |
| CN114335758A (en) * | 2021-12-31 | 2022-04-12 | 郑州大学 | Garnet solid electrolyte based high-temperature molten lithium iodine battery |
| CN114335758B (en) * | 2021-12-31 | 2023-03-17 | 郑州大学 | Garnet solid electrolyte based high-temperature molten lithium iodine battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106159318A (en) | Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof | |
| WO2013022034A1 (en) | Composite positive electrode active substance, all-solid-state cell, and method for producing composite positive electrode active substance | |
| KR20180015841A (en) | All solid lithium secondary battery comprising gel polymer electrolyte and method for manufacturing the same | |
| CN108172893B (en) | Lithium ion battery | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| CN102394305A (en) | Foamy copper oxide/copper lithium ion battery anode and preparation method thereof | |
| CN102427134A (en) | Mixed conductor composite material LiFePO4-MXy and preparation method thereof | |
| KR102204140B1 (en) | All-solid-state battery and manufacturing method thereof | |
| CN107706392B (en) | Preparation method of carbon-nitrogen co-coated sodium vanadium phosphate sodium ion battery positive electrode material | |
| CN1907844A (en) | High density ultrafine composite ferric lithium phosphate anode material and preparation method | |
| CN105938899A (en) | Preparation method and application of cathode material of fast ion conductor coated modified lithium ion battery | |
| CN104157909A (en) | Preparation method of lithium sulfur battery membrane electrode | |
| CN111697204B (en) | Lithium lanthanum zirconium oxide/lithium cobaltate composite material and preparation method and application thereof | |
| CN102315440A (en) | Spinel composite material, preparation method and application thereof | |
| CN108807920B (en) | LASO-coated octahedral-structure lithium nickel manganese oxide composite material and preparation method thereof | |
| CN103384001A (en) | Composite graphene electrode material and solid-phase catalysis preparation method thereof | |
| CN104966814A (en) | High-security metallic lithium cathode and preparation method thereof | |
| CN102339999B (en) | Polyanion composite material, its preparation method and application | |
| CN102263240A (en) | Lithium ion secondary battery, anode, and manufacturing method and charging and discharging method for anode | |
| JP2009064715A (en) | Positive electrode and lithium secondary battery using the same | |
| CN102104149A (en) | Lithium iron phosphate composite anode material in lithium-ion battery and preparation method thereof | |
| Gu et al. | Preparation of new composite electrolytes for solid-state lithium rechargeable batteries by compounding LiTFSI, PVDF-HFP and LLZTO | |
| Fu et al. | Li2Se as cathode additive to prolong the next generation high energy lithium-ion batteries | |
| CN103378355A (en) | Alkali metal secondary battery as well as negative active substance, negative material and negative electrode thereof, and preparation method of negative active substance | |
| Zhang et al. | Enhanced high-voltage cycling stability of nickel-rich cathode materials by surface modification using LaFeO 3 ionic conductor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161123 |
|
| WD01 | Invention patent application deemed withdrawn after publication |