CN116565299A - Multifunctional composite ceramic nanowire, solid electrolyte, battery and preparation method of multifunctional composite ceramic nanowire - Google Patents
Multifunctional composite ceramic nanowire, solid electrolyte, battery and preparation method of multifunctional composite ceramic nanowire Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000000919 ceramic Substances 0.000 title claims abstract description 78
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910021526 gadolinium-doped ceria Inorganic materials 0.000 claims abstract description 64
- 239000003792 electrolyte Substances 0.000 claims abstract description 43
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- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 15
- 229910020719 Li0.33 La0.56 Inorganic materials 0.000 claims abstract description 7
- 239000002033 PVDF binder Substances 0.000 claims description 37
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 23
- 238000001523 electrospinning Methods 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 159000000002 lithium salts Chemical class 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 12
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- 229910013553 LiNO Inorganic materials 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
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- 229910010941 LiFSI Inorganic materials 0.000 claims 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical group [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 21
- 229910001416 lithium ion Inorganic materials 0.000 description 21
- 230000005012 migration Effects 0.000 description 16
- 238000013508 migration Methods 0.000 description 16
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- 150000002500 ions Chemical class 0.000 description 7
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 238000010494 dissociation reaction Methods 0.000 description 6
- 230000005593 dissociations Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- 239000007774 positive electrode material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
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Abstract
A multifunctional composite ceramic nanowire, a solid electrolyte, a battery and a preparation method thereof are provided, wherein the multifunctional composite ceramic nanowire comprises a functional ceramic with a one-dimensional continuous structure and zero-dimensional granular functional ceramic uniformly distributed on the functional ceramic, and the functional ceramic is one-dimensional Li 0.33 La 0.56 TiO 3‑x (LLTO) nanowires, the zero-dimensional granular functional ceramic being gadolinium doped cerium oxide (Gd) 0.1 Ce 0.9 O 1.9 (GDC). The electrochemical performance of the composite solid electrolyte taking the composite ceramic nanowire as the filler and the compatibility with the electrode are obviously improved. Cycle performance and rate of solid-state battery using the solid-state electrolyteThe performance is obviously improved, and meanwhile, the stability between the polymer matrix electrolyte and the anode and the cathode is obviously improved.
Description
Technical Field
The invention relates to a solid-state battery technology, in particular to a multifunctional composite ceramic nanowire, a solid-state electrolyte, a battery and a preparation method thereof.
Background
With the progress of portable electronic devices and the popularization of new energy automobiles, energy storage systems with high safety and high energy density are receiving a great deal of attention. Compared with the traditional lithium ion battery, the solid lithium metal battery replaces the inflammable and volatile electrolyte component in the lithium ion battery, and uses the solid electrolyte with higher safety; meanwhile, the solid electrolyte has better compatibility with lithium metal than electrolyte, so the lithium metal with extremely high specific capacity (3860 mA h g -1 ). Considering the two points comprehensively, the solid-state lithium metal battery is a type of energy storage form with high safety and high energy density.
As a key component of the solid lithium metal battery, the solid electrolyte mainly includes two forms of an inorganic solid electrolyte and a polymer-based solid electrolyte. Polymer-based solid electrolytes have been widely studied for their better processability, positive and negative electrode interface contact properties, and relatively low cost compared to ceramic electrolytes. However, the polymer solid electrolyte has room temperature ionic conductivityThe disadvantages of low migration number of lithium ions, poor stability of the interface between electrolyte and anode and the interface between anode and cathode, poor mechanical properties and the like greatly restrict the performance of the polymer-based solid-state battery under the condition of high multiplying power at room temperature. Thus, good compatibility of electrolyte/electrode interface is achieved in solid state battery and free Li inside polymer solid state electrolyte is promoted + Is a key to achieving excellent rate performance and cycle performance of solid state lithium metal batteries.
PVDF as a common polymer solid electrolyte matrix with internal Li + The transmission mechanism is as follows: [ Li (DMF) x ] + Movement is transmitted both intra-and inter-chain within PVDF molecules. However, the room temperature ionic conductivity of PVDF electrolyte (-2X 10) -4 S cm -1 ) The migration number (about 0.2) of lithium ions and the dissociation degree of lithium salt are low, and the interfacial compatibility of DMF molecules remained in the electrolyte to the anode and the cathode is poor; these greatly limit the cycling and rate performance of solid state batteries using PVDF electrolytes.
It should be noted that the information disclosed in the above background section is only for understanding the background of the present application and thus may include information that does not form the prior art that is already known to those of ordinary skill in the art.
Disclosure of Invention
The main object of the present invention is to overcome the above-mentioned drawbacks of the background art and to provide.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a multifunctional composite ceramic nanowire comprises a functional ceramic with a one-dimensional continuous structure and zero-dimensional granular functional ceramic uniformly distributed on the functional ceramic, wherein the functional ceramic is one-dimensional Li 0.33 La 0.56 TiO 3-x (LLTO) nanowires, the zero-dimensional granular functional ceramic being gadolinium doped cerium oxide (Gd) 0.1 Ce 0.9 O 1.9 (GDC)。
A method for preparing the multifunctional composite ceramic nanowire, comprising the following steps:
gd is put into 0.1 Ce 0.9 O 1.9 (GDC) particles are uniformly dispersed inFor preparing Li 0.33 La 0.56 TiO 3-x (LLTO) precursor solution of the nanowire to obtain mixed solution, and then preparing a composite ceramic nanowire precursor by using the mixed solution through an electrostatic spinning technology; after calcination, the GDC@LLTO composite ceramic nanowire is prepared.
Further, the method specifically comprises the following steps:
LiNO is to be carried out 3 And La (NO) 3 ) 3 ·6H 2 O is dissolved in a mixed solution of DMF and acetic acid; then adding a proper amount of GDC nano powder, and uniformly dispersing; then PVP is added to adjust the solution viscosity, tetrabutyl titanate is added, and the mixture is fully stirred to obtain an electrospinning liquid;
electrospinning by using the electrospinning liquid to prepare a GDC@LLTO nanowire precursor;
calcining the GDC@LLTO nanowire precursor at 750-900 ℃; and then naturally cooling to obtain the GDC@LLTO composite ceramic nanowire.
A composite solid state electrolyte comprising a lithium salt, a polymer matrix, and a filler comprising one of GDC particles, LLTO nanowires, and gdc@llto composite ceramic nanowires.
Further, the polymer matrix is PVDF.
Further, the lithium salt is LiFSI.
A method of preparing the composite solid electrolyte comprising the steps of:
dissolving a lithium salt in a DMF solution;
adding the filler comprising GDC@LLTO composite ceramic nanowires to the solution, and uniformly dispersing;
adding the powder of the polymer matrix, and uniformly stirring;
casting the solution into a container, and drying.
A lithium metal battery has the composite solid electrolyte.
The invention has the following beneficial effects:
the invention provides a multifunctional composite ceramic nanowire, which comprises a one-dimensional continuous junctionStructured functional ceramic Li 0.33 La 0.56 TiO 3-x (LLTO) nanowires and zero-dimensional particulate functional ceramic Gd homogeneously distributed thereon 0.1 Ce 0.9 O 1.9 (GDC) as filler, continuous Li can be built up in a polymer matrix electrolyte, in particular a PVDF matrix electrolyte + The transmission channel improves the ion transport efficiency; meanwhile, the dissociation degree of lithium salt and the migration number of lithium ions in the electrolyte are improved, and lithium deposition is uniform so as to prolong the cycle life of the battery. The multifunctional composite ceramic nanowire is used as a filler to be added into polymer matrix electrolyte, particularly PVDF matrix electrolyte, and the room-temperature ion conductivity, the lithium ion migration number and the electrochemical window of the formed composite solid electrolyte are all obviously improved. The cycling stability of the Li/Li symmetrical battery prepared by the composite solid electrolyte is obviously enhanced; the NCM811/Li solid state battery is excellent in cycle and rate performance. The invention has wide application prospect in the field of solid lithium metal batteries.
In a preferred embodiment, the multifunctional composite ceramic nanowire is used as a filler of the solid electrolyte, the LLTO one-dimensional nanowire constructs a continuous lithium ion transmission channel in the PVDF polymer solid electrolyte, zero-dimensional particles GDC are grown on the surface of the LLTO one-dimensional nanowire, the GDC is used as oxygen-enriched vacancy ceramic, the oxygen vacancies have positive electricity, lithium salt anions can be effectively fixed, the migration number of lithium ions is improved, and the dissociation of lithium salts is promoted. The electrochemical performance of the composite solid electrolyte taking the GDC@LLTO composite ceramic nanowire as a filler and the compatibility with an electrode are obviously improved, and the method has important significance for improving the electrochemical performance of the PVDF-based electrolyte.
The solid electrolyte provided by the invention can be well matched with a lithium metal anode and an NCM811 anode, and the addition of the GDC@LLTO composite ceramic nanowire in the solid electrolyte can obviously improve the cycle performance and the multiplying power performance of a solid battery using the solid electrolyte, and meanwhile, the stability between a polymer matrix electrolyte, particularly a PVDF electrolyte, and the anode and the cathode is obviously improved. Therefore, the invention has great significance for realizing the long-time circulation of the lithium metal battery at room temperature and has high application value.
Drawings
A in fig. 1 is an SEM photograph of LLTO nanowires prepared in example 1 of the present invention; b in fig. 1 is a large-scale SEM photograph of LLTO nanowires prepared in example 1 and a mapping photograph of O, ti and La elements.
Fig. 2 is an XRD pattern of LLTO nanowires prepared in example 1.
FIG. 3 is an XRD of the GDC@LLTO composite ceramic nanowires prepared in example 2 at different calcination temperatures.
A in fig. 4 is the mass ratio of GDC to LLTO of 5 in example 2: SEM pictures of 95 composite ceramic nanowires; b in fig. 4 is the mass ratio of GDC to LLTO of 10 in example 2: SEM pictures of 90 composite ceramic nanowires; c in fig. 4 is the mass ratio of GDC to LLTO of 15 in example 2: SEM pictures of 85 composite ceramic nanowires; d in FIG. 4 is the mass ratio of GDC to LLTO of 20 in example 2: SEM pictures of 80 composite ceramic nanowires.
A in fig. 5 is an optical photograph of the PVDF solid electrolyte membrane prepared in example 3; b in fig. 5 is a scanned photograph of the PVDF solid electrolyte membrane prepared in example 3.
A in fig. 6 is an optical photograph of the PVLG solid electrolyte membrane prepared in example 4; b in fig. 6 is a scanned photograph of the PVLG solid electrolyte membrane prepared in example 4.
FIG. 7 is the electrochemical performance of the assembled NCM811/PVDF/Li, NCM811/PVG/Li, NCM811/PVL/Li and NCM811/PVLG/Li solid state batteries of example 7.
Detailed Description
The following describes embodiments of the present invention in detail. It should be emphasized that the following description is merely exemplary in nature and is in no way intended to limit the scope of the invention or its applications.
In some embodiments, the present invention provides a multifunctional composite ceramic nanowire comprising a functional ceramic of one-dimensional continuous structure and a zero-dimensional particulate functional ceramic uniformly distributed thereon. The functional ceramic is one-dimensional Li 0.33 La 0.56 TiO 3-x (LLTO) nanowire, a material for constructing ion transmission channels in polymer electrolyte, has high room temperature ion conductivity (-10) -3 S cm -1 ) The LLTO nanowire can construct an efficient ion transport channel in a polymer solid electrolyte. The zero-dimensional granular functional ceramic is gadolinium doped cerium oxide Gd 0.1 Ce 0.9 O 1.9 The (GDC) is a material for promoting the dissociation of lithium salt in polymer electrolyte, and can be used as oxygen-enriched vacancy ceramic, so that anions of lithium salt for a lithium battery can be effectively fixed, the migration number of lithium ions is increased, and the dissociation of the lithium salt is promoted. The multifunctional composite ceramic nanowire is called as GDC@LLTO composite ceramic nanowire, and the electrochemical performance of the composite solid electrolyte using the multifunctional composite ceramic nanowire as a filler and the performance of the composite solid electrolyte in a solid battery are obviously improved.
Illustratively, the micro-morphology of the multifunctional composite ceramic nanowire is shown in (b) of fig. 4, zero-dimensional particles grow on the surface of the one-dimensional nanowire of the composite ceramic, the micro-morphology is rough, the diameter of the nanowire is about 200nm, and the continuity is good. The room temperature ion conductivity, the lithium ion migration number and the electrochemical window of the composite solid electrolyte prepared by adding the composite solid electrolyte serving as the filler into the polyvinylidene fluoride matrix are all remarkably improved. The cycle stability of the Li/Li symmetrical battery prepared by using the method is obviously enhanced; the NCM811/Li solid state battery is excellent in cycle and rate performance. The invention has wide application prospect in the field of solid lithium metal batteries.
In some embodiments, the invention provides a method for preparing a multifunctional composite ceramic nanowire, comprising the following steps:
gd is put into 0.1 Ce 0.9 O 1.9 (GDC) particles are homogeneously dispersed for Li preparation 0.33 La 0.56 TiO 3-x (LLTO) precursor solution of the nanowire to obtain mixed solution, and then preparing a composite ceramic nanowire precursor by using the mixed solution through an electrostatic spinning technology; finally, a muffle furnace can be used for calcining at a proper temperature to prepare the multifunctional composite ceramic nanowire. The prepared product is Gd 0.1 Ce 0.9 O 1.9 (GDC) nanoparticle distribution in Li 0.33 La 0.56 TiO 3-x GDC@LLTO composite ceramic nanowires on (LLTO) nanowires.
In a preferred embodiment, the preparation method of the multifunctional composite ceramic nanowire specifically comprises the following steps:
s1: proper amount of LiNO 3 And La (NO) 3 ) 3 ·6H 2 O is dissolved in a mixed solution of DMF (N, N-dimethylformamide) and acetic acid; then adding a proper amount of GDC nano powder, and uniformly dispersing by ultrasonic; then, polyvinylpyrrolidone (PVP) is added to adjust the solution viscosity; and finally, adding tetrabutyl titanate into the mixture, and fully stirring the mixture to form pale yellow uniform slurry to obtain the electrospinning liquid.
S2: using the above-mentioned electrospinning liquid, electrospinning voltage is-1-20 kV, liquid advancing rate is 1mL h -1 The distance between the needle and the receiving drum was 15cm, the temperature was 34 ℃, and the ambient humidity was 55%. Electrospinning under the parameters described above produced gdc@llto nanowire precursors.
S3: placing GDC@LLTO nanowire precursor in a porcelain boat of alumina at 1 ℃ for min -1 The temperature rise rate of the furnace is increased from room temperature to 280 ℃, and the furnace is kept for 2 hours; then, at 5 ℃ for min -1 The temperature rise rate of the furnace is increased from 280 ℃ to 900 ℃, and the furnace is insulated for 3 hours; and finally, naturally cooling to room temperature to obtain the GDC@LLTO nanowire.
The invention successfully prepares the GDC@LLTO composite ceramic nanowire by using the precursor of the rapid lithium ion conductor ceramic LLTO and the GDC nano powder. LLTO has high room temperature ion conductivity, and can be used as a filler to construct a continuous lithium ion transmission channel in PVDF polymer solid electrolyte; the GDC is used as oxygen-enriched vacancy ceramic, and oxygen vacancies have electropositivity, so that lithium salt anions can be effectively fixed, the migration number of lithium ions is increased, and the dissociation of lithium salts is promoted. The electrochemical performance of the composite solid electrolyte taking the GDC@LLTO composite ceramic nanowire as a filler and the compatibility with an electrode are obviously improved, and the method has important significance for improving the electrochemical performance of the solid battery polymer matrix electrolyte such as PVDF-based electrolyte.
Thus, embodiments of the present invention also provide a composite solid state electrolyte comprising a lithium salt, a polymer matrix, and a filler comprising GDC@LLTO composite ceramic nanowires.
In some embodiments, the polymer matrix of the composite solid state electrolyte is PVDF (polyvinylidene fluoride) and the lithium salt is LiFSI (lithium bis-fluorosulfonyl imide). The electrolyte may be prepared by casting and drying.
The composite solid electrolyte provided by the invention can be well matched with a lithium metal negative electrode and an NCM811 positive electrode, and the addition of the GDC@LLTO composite ceramic nanowire in the solid electrolyte can obviously improve the cycle performance and the rate performance of a solid battery using the solid electrolyte, and the application value is higher.
The embodiment of the invention also provides a lithium metal battery with the composite solid electrolyte.
Still another composite solid state electrolyte is provided that includes a lithium salt, a polymer matrix, and a filler that includes LLTO nanowires or GDC particles.
In a preferred embodiment, the preparation process of the LLTO nanowire comprises the following steps:
s1: proper amount of LiNO 3 (lithium nitrate), la (NO) 3 ) 3 ·6H 2 O (lanthanum nitrate hexahydrate) is dissolved in a mixed solution of DMF (N, N-dimethylformamide) and acetic acid; then, polyvinylpyrrolidone (PVP) is added to enable the solution to reach proper viscosity; and finally, adding tetrabutyl titanate, and fully stirring to obtain the electrospinning liquid.
S2: using the above-mentioned electrospinning liquid, electrospinning voltage is-1-20 kV, liquid advancing rate is 1mL h -1 The distance between the needle and the receiving drum was 15cm, the temperature was 34 ℃, and the ambient humidity was 55%. Electrospinning under the parameters described above produced LLTO nanowire precursors.
S3: placing LLTO nanowire precursor in a porcelain boat of aluminum oxide at 1 ℃ for min -1 The temperature rise rate of the furnace is increased from room temperature to 280 ℃, and the furnace is kept for 2 hours; then, at 5 ℃ for min -1 The temperature rise rate of the furnace is increased from 280 ℃ to 900 ℃, and the furnace is insulated for 3 hours; and finally, naturally cooling to room temperature to obtain the LLTO nanowire.
The present invention also provides a lithium metal battery having a composite solid state electrolyte including the LLTO nanowires.
Example 1
The implementation provides a preparation method of the LLTO nanowire:
LLTO ceramic nanowires were prepared using a sol-gel process, the specific preparation steps being as follows:
s1: 0.1311g LiNO 3 ，1.19g La(NO 3 ) 3 ·6H 2 O was dissolved in a mixed solution of 7.5mL DMF and 1.5mL acetic acid;
s2: 0.6g PVP was added to the solution of S1 and stirred for 3 hours;
s3: adding 1.7g of tetrabutyl titanate into the solution of S2, and stirring for 12 hours to prepare a pale yellow clear and transparent solution;
s4: electrospinning voltage-1-20 kV and pushing speed 1mL h -1 The distance between the needle and the receiving drum was 15cm, the electrospinning temperature was 34℃and the ambient humidity was 55%. Electrospinning the LLTO precursor slurry under the parameters described above to prepare LLTO nanowire precursors;
s5: placing LLTO nanowire precursor in a porcelain boat of aluminum oxide at 1 ℃ for min -1 The temperature rise rate of the furnace is increased from room temperature to 280 ℃, and the furnace is kept for 2 hours;
s6: at 5 ℃ for min -1 The temperature rise rate of the furnace is increased from 280 ℃ to 900 ℃, and the furnace is insulated for 3 hours; and finally, naturally cooling to room temperature to obtain the LLTO nanowire.
The experimental results are shown in FIGS. 1 a-b, and SEM photographs of LLTO nanowires show that the diameter of the nanowires is about 500nm; high-magnification SEM pictures of LLTO can observe loose porosity of LLTO nanowire surfaces. The energy dispersive X-ray spectrometer (EDS) spectroscopy test results of the LLTO nanowires showed that O, ti and La elements were uniformly distributed in the nanowires. The LLTO nanowire shown in FIG. 2 has an X-ray diffraction (XRD) pattern well matched with PDF #45-0465 and a tetragonal phase structure, which indicates that the prepared LLTO nanowire is pure phase.
Example 2
The example provides a preparation method of a GDC@LLTO composite ceramic nanowire:
s1: proper amount of 0.05g LiNO 3 And 0.396g La (NO) 3 ) 3 ·6H 2 O was dissolved in a mixed solution of 2.5mL DMF and 0.5mL acetic acidIn (a) and (b);
s2: adding a proper amount of GDC nano powder into the solution of S1, and uniformly dispersing by ultrasonic;
s3: adding 0.6g PVP to the S2 to adjust the solution viscosity;
s4: adding 0.567g of tetrabutyl titanate into the S3, and fully stirring to prepare pale yellow uniform slurry;
s5: using the above-mentioned electrospinning liquid, electrospinning voltage is-1-20 kV, liquid advancing rate is 1mL h -1 The distance between the needle and the receiving drum was 15cm, the temperature was 34 ℃, and the ambient humidity was 55%. Electrospinning under the parameters described above produced gdc@llto nanowire precursors.
S6: placing GDC@LLTO nanowire precursor in a porcelain boat of alumina at 1 ℃ for min -1 The temperature rise rate of the furnace is increased from room temperature to 280 ℃, and the furnace is kept for 2 hours;
s7: at 5 ℃ for min -1 The temperature rising rate of the catalyst is increased from 280 ℃ to a certain calcination temperature, and the catalyst is kept at the temperature for 3 hours; and finally, naturally cooling to room temperature to obtain the GDC@LLTO nanowire.
In this example, the effect of different calcination temperatures on the GDC@LLTO nanowire phase was first tried. When the GDC content in the composite nanowire is 10wt%, the XRD patterns of the GDC@LLTO nanowire with 750, 800, 850 and 900 ℃ as the calcination temperature are shown in figure 3. The nanowire calcination temperatures at 750, 800 and 850 ℃ showed distinct hetero peaks at 26.3 and 27.1 °, corresponding to Li, respectively 2 TiO 3 (PDF#33-0381) and La 2 Ti 2 O 7 (PDF # 70-1690). When the calcination temperature is 900 ℃, the impurity peak disappears, and the GDC@LLTO composite ceramic nanowire is in a pure phase.
Meanwhile, the influence of the content of GDC on the morphology of the composite nanowire is explored. Fig. 4 is an SEM image of composite ceramic nanowires corresponding to different GDC to LLTO mass ratios. When the mass ratio of GDC to LLTO is 5: at 95, the composite ceramic nanowire has a smoother surface, a diameter of about 170nm and a uniform morphology; when the mass ratio is 10: at 90, small particles grow on the surface of the composite nanowire, the roughness is uneven, the diameter of the nanowire is about 200nm, and the continuity is good; and when the mass ratio is 15:85, the nanowire is in a strip shape, the diameter is not uniform, and the nanowire is broken; continuing to increase the GDC duty cycle to a mass ratio of 20:80, the surface of the nanowire is composed of a plurality of tiny particles, and the diameter of the nanowire reaches about 1 mu m. Considering phases and microscopic morphologies comprehensively, the composition ratio of the preferred nanowire is determined as a mass ratio of GDC to LLTO of 1:9, the calcination temperature was 900 ℃.
Example 3
The example provides a method for preparing PVDF polymer solid electrolyte, which comprises the following steps:
s1: 0.276g LiFSI was completely dissolved in 15mL of DMF solution;
s2: 0.4g of PVDF powder (mw=300,000) was added to S2 and stirred for 6 hours;
s3: casting the solution in S3 into a glass dish with the diameter of 10 cm;
s4: the mixture was dried in a forced air oven at 55℃for 24 hours to prepare a pale yellow solid electrolyte, which was cut into 19mm diameter discs for use.
Fig. 5a is an optical photograph of a PVDF electrolyte, which appears white and has a flat surface. Obvious PVDF spherulites were observed for SEM pictures of PVDF electrolyte, with loose porous surfaces (fig. 5 b). The room temperature ionic conductivity of PVDF electrolyte prepared by the method is 3.69×10 -4 S cm -1 The migration number of lithium ions is 0.24, the oxidation resistance window is 4.1V, and the activation energy of lithium ion migration is 0.31eV.
Example 4
The present example provides a method for preparing a PVDF-based composite solid electrolyte (PVLG):
s1: 0.276g LiFSI was completely dissolved in 15mL of DMF solution;
s2: adding 60mg of GDC@LLTO nanowire into the S1, and uniformly dispersing by ultrasonic waves;
s3: 0.4g of PVDF powder (mw=300,000) was added to S2 and stirred for 6 hours;
s4: casting the solution in S3 into a glass dish with the diameter of 10 cm;
s5: the mixture was dried in a forced air oven at 55℃for 24 hours to prepare a pale yellow solid electrolyte, which was cut into 19mm diameter discs for use.
As shown in fig. 6 a-b, the PVLG electrolyte is yellowish, gdc@llto nanowires are distributed in the voids of the PVDF solid electrolyte, and the surface is relatively dense. The PVLG electrolyte prepared by the method has the room temperature ion conductivity of 8.71 multiplied by 10 -4 S cm -1 The migration number of lithium ions is 0.66, the oxidation resistance window is 4.5V, and the activation energy of lithium ion migration is 0.24eV.
Example 5
The present example provides a method for preparing a PVDF-based composite solid electrolyte (PVG):
s1: 0.276g LiFSI was completely dissolved in 15mL of DMF solution;
s2: adding 60mg of GDC nano particles into the S1, and uniformly dispersing by ultrasonic waves;
s3: 0.4g of PVDF powder (mw=300,000) was added to S2 and stirred for 6 hours;
s4: casting the solution in S3 into a glass dish with the diameter of 10 cm;
s5: the mixture was dried in a forced air oven at 55℃for 24 hours to prepare a pale yellow solid electrolyte, which was cut into 19mm diameter discs for use.
The PVG electrolyte prepared by the method has room temperature ionic conductivity of 3.61 multiplied by 10 -4 S cm -1 The number of lithium ion migration was 0.51, and the activation energy of lithium ion migration was 0.28eV.
Example 6
The present example provides a method for preparing a PVDF-based composite solid electrolyte (PVL):
s1: 0.276g LiFSI was completely dissolved in 15mL of DMF solution;
s2: adding 60mg of LLTO nanowires into the S1, and uniformly dispersing by ultrasonic waves;
s3: 0.4g of PVDF powder (mw=300,000) was added to S2 and stirred for 6 hours;
s4: casting the solution in S3 into a glass dish with the diameter of 10 cm;
s5: the mixture was dried in a forced air oven at 55℃for 24 hours to prepare a pale yellow solid electrolyte, which was cut into 19mm diameter discs for use.
Room temperature ions of PVL electrolyte prepared by the methodConductivity of 4.37X10 -4 S cm -1 The number of lithium ion migration was 0.38, and the activation energy of lithium ion migration was 0.29eV.
Example 7
In this example, a method for preparing a solid-state battery using a PVDF-based solid-state electrolyte is provided:
s1: positive electrode active material NCM811, conductive agent Super P, and binder PVDF 5130 in mass ratio of 8:1:1 is dispersed in N-methyl-2-pyrrolidone (NMP) to prepare uniform slurry;
s2: uniformly scraping the slurry on the aluminum foil; then, it was placed in a vacuum oven at 120 ℃ and dried for 3 hours;
s3: the positive electrode active material is pressed into a wafer with the thickness of 12mm by a sheet pressing machine, and the positive electrode active material loading amount is 1.4mg cm -2 ；
S4: the positive electrode in S3 was used, the negative electrode was lithium metal with a diameter of 15mm, and the electrolyte was PVDF, PVLG, PVG and PVL electrolyte prepared in examples 3 to 6, respectively, to prepare a CR2032 button cell in an argon glove box.
The cycle performance test was performed on NCM811/PVDF/Li, NCM811/PVG/Li, NCM811/PVL/Li, and NCM811/PVLG/Li solid-state batteries assembled in this example, respectively. As shown in fig. 7, the solid-state battery using the PVLG electrolyte in example 4 can stably operate for 1500 cycles at a charge-discharge rate of 2C, while the solid-state battery assembled with other types of electrolytes all exhibit a significant capacity fade phenomenon. This demonstrates that the improvement of electrochemical performance of the GDC@LLTO composite ceramic nanowire to PVDF electrolyte is obvious; meanwhile, the stability between PVDF electrolyte and positive and negative electrodes is obviously improved. The test result shows that the invention has important significance for realizing the long-cycle at room temperature of the lithium metal battery.
The background section of the present invention may contain background information about the problems or environments of the present invention and is not necessarily descriptive of the prior art. Accordingly, inclusion in the background section is not an admission of prior art by the applicant.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention. In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "preferred embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Those skilled in the art may combine and combine the features of the different embodiments or examples described in this specification and of the different embodiments or examples without contradiction. Although embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope of the invention as defined by the appended claims.
Claims (8)
1. A multifunctional composite ceramic nanowire is characterized by comprising a functional ceramic with a one-dimensional continuous structure and zero-dimensional granular functional ceramic uniformly distributed on the functional ceramic, wherein the functional ceramic is one-dimensional Li 0.33 La 0.56 TiO 3-x (LLTO) nanowires, the zero-dimensional granular functional ceramic being gadolinium doped cerium oxide (Gd) 0.1 Ce 0.9 O 1.9 (GDC)。
2. A method of making the multifunctional composite ceramic nanowire of claim 1, comprising the steps of:
gd is put into 0.1 Ce 0.9 O 1.9 (GDC) particles are homogeneously dispersed for Li preparation 0.33 La 0.56 TiO 3-x (LLTO) precursor solution of the nanowire to obtain mixed solution, and then preparing a composite ceramic nanowire precursor by using the mixed solution through an electrostatic spinning technology; after calcination, the GDC@LLTO composite ceramic nanowire is prepared.
3. The method according to claim 2, characterized in that it comprises in particular the following steps:
LiNO is to be carried out 3 And La (NO) 3 ) 3 ·6H 2 O is dissolved in a mixed solution of DMF and acetic acid; then adding a proper amount of GDC nano powder, and uniformly dispersing; then PVP is added to adjust the solution viscosity, tetrabutyl titanate is added, and the mixture is fully stirred to obtain an electrospinning liquid;
electrospinning by using the electrospinning liquid to prepare a GDC@LLTO nanowire precursor;
calcining the GDC@LLTO nanowire precursor at 750-900 ℃ to prepare the GDC@LLTO composite ceramic nanowire.
4. A composite solid state electrolyte comprising a lithium salt, a polymer matrix, and a filler comprising one of GDC particles, LLTO nanowires, and gdc@llto composite ceramic nanowires.
5. The composite solid state electrolyte of claim 4 wherein the polymer matrix is PVDF.
6. The composite solid state electrolyte of claim 4 or 5 wherein the lithium salt is LiFSI.
7. A method of preparing the composite solid electrolyte of any one of claims 4 to 6, comprising the steps of:
dissolving a lithium salt in a DMF solution;
adding the filler comprising GDC@LLTO composite ceramic nanowires to the solution, and uniformly dispersing;
adding the powder of the polymer matrix, and uniformly stirring;
casting the solution into a container, and drying.
8. A lithium metal battery having the composite solid electrolyte according to any one of claims 4 to 6.
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