CN113851705A - Method for modifying all-solid-state lithium ion battery interface by using two-dimensional titanium carbide-acetylene black - Google Patents
Method for modifying all-solid-state lithium ion battery interface by using two-dimensional titanium carbide-acetylene black Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 73
- 239000006230 acetylene black Substances 0.000 title claims abstract description 65
- 239000010936 titanium Substances 0.000 title claims abstract description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 81
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 45
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 19
- 239000007784 solid electrolyte Substances 0.000 abstract description 19
- 210000001787 dendrite Anatomy 0.000 abstract description 14
- 230000004048 modification Effects 0.000 abstract description 14
- 238000012986 modification Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000002002 slurry Substances 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 28
- 230000010287 polarization Effects 0.000 description 22
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- 238000010586 diagram Methods 0.000 description 17
- 238000000151 deposition Methods 0.000 description 15
- 230000008021 deposition Effects 0.000 description 15
- 239000012528 membrane Substances 0.000 description 15
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 238000002715 modification method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000001453 impedance spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 1
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- 150000002641 lithium Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 method for modifying an interface of an all-solid-state lithium ion battery by utilizing two-dimensional titanium carbide-acetylene black aims to solve the problems of large resistance of a polymer electrolyte and a positive electrode interface and unstable solid electrolyte interface film. The method comprises the following specific steps: uniformly mixing acetylene black and two-dimensional titanium carbide according to the mass ratio of 1:1, adding electrolyte precursor slurry with the solid mass ratio of 5:2 to obtain interface modified slurry, coating a modified layer with the thickness of 50 mu m on an electrolyte by a blade coating method, and drying at 100 ℃ to obtain the electrolyte film with the interface modified layer. The two-dimensional titanium carbide-acetylene black is used as a polymer electrolyte modification layer, and an electrolyte interface is improved through a coating, so that the body impedance and the interface impedance of the polymer electrolyte are effectively reduced, a stable solid electrolyte interface layer is formed between the polymer electrolyte and a positive electrode, the influence of the formation of lithium dendrites on the performance of the battery is prevented, and the charge/discharge specific capacity and the capacity retention rate of the all-solid-state lithium ion battery are improved. The invention is used in the field of lithium ion batteries.
Description
Technical Field
The invention belongs to the field of all-solid-state lithium ion battery polymer electrolyte interface modification, and particularly relates to a method for modifying an all-solid-state lithium ion battery interface by using two-dimensional titanium carbide-acetylene black.
Background
In recent years, due to depletion of fossil energy, development and utilization of new energy sources such as solar energy, wind energy, and tidal energy have been actively pursued. Therefore, the lithium ion battery capable of efficiently storing electricity is produced at the same time, has the advantages of high energy density, high working voltage, low self-discharge rate and the like, and is widely applied to actual production and life. However, the occurrence of fire accident of electric vehicles is endless, and it is also revealed that the liquid lithium ion battery is easy to cause fire or explosion caused by liquid leakage, thermal runaway and the like, which limits its further popularization and application.
The solid-state lithium ion battery can perfectly solve the problems, but the problems of poor interface contact property, low room-temperature ionic conductivity and the like of the solid-state lithium ion battery are troubled. In addition, the lithium ion battery generally has the hidden trouble that lithium dendrite pierces through the diaphragm in the cycle process to cause battery short circuit and fire. Therefore, in the research process of the all-solid-state lithium ion battery, good contact between the polymer electrolyte and the electrode, uniform deposition of lithium ions on the positive electrode, formation of a stable solid electrolyte interface film and excellent room-temperature conductivity are all important problems to be solved.
Solid state lithium batteries have three main components: a cathode, an anode and a solid electrolyte. During discharge, lithium ions and electrons migrate in opposite directions, accompanied by cathodic reduction and anodic oxidation. The electrolyte interface in a solid state lithium ion battery involves the following reaction steps: (i) lithium ion diffusion in the electrolyte, (ii) charge transfer process, (iii) lithium ion diffusion in the electrode, (iv) interface reaction, and the like. A stable and intimate interface is required to ensure the smooth progress of the above reaction steps. Chen et al proposed a new strategy to improve interface stability by forming an electrolyte buffer layer on the rough surfaces of the electrode and solid electrolyte in 2020 (ACS appl. mater. interfaces 2020,12, 15120-15127). And the electrode/solid electrolyte was connected by coating the side of the electrolyte facing the lithium anode with a layer of graphite. The structure greatly improves the interface stability and reduces the interface impedance of the solid-state battery. The graphite buffer layer has obvious enhancement effect on interface contact and inhibition effect on lithium dendrite. The assembled solid-state battery shows good rate performance under 1C, 2C and 4C, and the electrode/electrolyte design method shows good application prospect in the solid-state lithium battery. In addition to solid electrolyte modification, cathode surface modification is another effective method to mitigate interfacial degradation. Yang et al synthesized a continuous compact Lithium Aluminum Titanium Phosphate (LATP) coating on the surface of lithium cobaltate by low temperature treatment (j.power source 2018,3,388, 65-70). The solid lithium ion battery assembled by the PEO-based polymer electrolyte and the LATP modified lithium cobaltate shows high capacity retention (93.2% after 50 cycles) at 4.2V, which shows that the modified coating can effectively enhance the cycle stability of the PEO-based polymer electrolyte. A stable interface is critical to the electrochemical performance of solid-state lithium-ion batteries. Most studies have focused on modifying the lithium positive electrode to inhibit lithium dendrites. It can be seen that controlling the electrode/electrolyte interfacial stability is very important to improve the electrochemical performance of the cell.
Disclosure of Invention
The invention provides a method for modifying an all-solid-state lithium ion battery interface by using two-dimensional titanium carbide-acetylene black, aiming at the problems of poor and unstable modification of a polymer electrolyte interface in the prior art. The modified polymer electrolyte membrane has greater ionic conductivity, less impedance and lower activation energy than the original polymer electrolyte membrane, exhibits sufficient binding of the positive electrode to the surface of the polymer electrolyte membrane when the assembled half cell is cycled, and stabilizes the rapid formation of an SEI film. The modified polymer electrolyte membrane prepared by the method can improve the charge/discharge specific capacity and the cycling stability of the corresponding all-solid-state lithium ion battery.
The object of the present invention can be achieved by the following method: a method for modifying an interface of an all-solid-state lithium ion battery by utilizing two-dimensional titanium carbide (MXene) and acetylene black is characterized by comprising the specific steps of uniformly mixing the two-dimensional titanium carbide and the acetylene black, adding a polymer electrolyte precursor solution, adjusting the solution to a proper concentration by using an organic solvent, uniformly stirring, preparing a layer of modified coating on the surface of a polymer electrolyte by adopting a blade coating method, and drying in an oven to prepare the polymer electrolyte with the two-dimensional titanium carbide-acetylene black modified interface layer;
the mass ratio of the two-dimensional titanium carbide to the acetylene black is 1-4:1-4, and the two-dimensional titanium carbide and the acetylene black have excellent conductivity, so that the modified interface layer has double-carrier characteristics of ion conduction and conduction on the premise of ion conduction of a polymer electrolyte, so that power lines are uniformly distributed, local excessive lithium ions are eliminated, and the lithium ions are uniformly deposited on the surface of a negative electrode. However, due to the polarization of the interface layer, when current passes through the electrode, an equivalent resistor is connected in series between the electrode and the electrolyte interface, the value of the equivalent resistor is equivalent to the polarization degree, the current density passing through the negative electrode close to the positive electrode is high, the polarization value of the negative electrode is also high, and the voltage drop caused by polarization is also large, so that the actual current density at each position on the whole negative electrode surface tends to be uniform, a uniform lithium deposition layer is obtained, and the uniform deposition capability can be improved by improving the polarization degree of the negative electrode;
the mass ratio of the two-dimensional titanium carbide and acetylene black mixed solid to the polymer electrolyte precursor liquid is 1-5:5, the polymer electrolyte with the mixed conducting layer is prepared, and when other conditions are determined, if the conductivity of the electrolyte is large, namely the conducting capacity is strong, the difference of solution voltage between the anode and the cathode is small, so that the adjustment can be easily realized through the polarization of the cathode, and the current density is uniformly distributed on the anode; if the polarization degree of the electrolyte is small and even approaches zero, the conductivity of the electroplating solution is increased, and the uniform deposition capacity and the deep deposition capacity cannot be improved greatly, so that the electrolyte with good conductivity and the modified layer with large polarization function are required to form the polymer electrolyte of the mixed conducting layer;
the organic solvent with the adjusted concentration comprises one or more of N-methyl pyrrolidone, N, N-dimethyl formamide or N, N-dimethyl acetamide, and an effective solvent for preparing a polymer electrolyte precursor solution is obtained;
the method is characterized in that an organic solvent is dripped at a speed of 20 drops/min to prevent the wall hanging of medicines from causing the uneven solution of a polymer electrolyte precursor, the stirring time is 8-14h, the dripping speed and the stirring are one of key factors for obtaining an even modified coating, and the dripping speed and the stirring are combined with the polymer electrolyte and the modified coating to form a combined compatibility to prepare the even modified coating, so that the current density of lithium ion deposition is even, lithium dendrites are eliminated, a spherical lithium metal deposition layer is generated, a diaphragm cannot be punctured, and the safety and the long service life of the lithium ion solid-state battery are ensured;
further limiting, the method for modifying the interface of the all-solid-state lithium ion battery by using the two-dimensional titanium carbide-acetylene black is characterized in that the thickness of the modified coating is 10-50 μm, and the thickness can ensure the uniformity and smoothness of the modified coating, form good polarization resistance, balance current density, enable lithium ions to be uniformly deposited and form a spherical lithium ion deposition shape;
the vacuum drying temperature of the polymer electrolyte is 100-120 ℃, the vacuum drying temperature is higher than the boiling point temperature of the solvent and is greatly lower than the decomposition temperature of the electrolyte, so that the solvent in the polymer electrolyte is completely evaporated to form the all-solid-state electrolyte, micropores are formed during evaporation, a lithium ion transmission channel is formed, the conductivity of the all-solid-state polymer electrolyte is improved, and the stability of the polymer electrolyte is ensured.
And the method for modifying the interface of the all-solid-state lithium ion battery by using the two-dimensional titanium carbide-acetylene black is characterized in that the two-dimensional titanium carbide is titanium aluminum carbide (Ti)3AlC2) Obtained by etching hydrofluoric acid, wherein the hydrofluoric acid reacts with aluminum oxide on the surface and then with metallic aluminum in the reaction process, and the metallic aluminum can be dissolved in the hydrofluoric acid to generate [ AlF ]6]3-Thereby etching the aluminum in the titanium aluminum carbide to form the organ-structured two-dimensional titanium carbide.
The hydrofluoric acid is prepared from lithium fluoride and hydrochloric acid, and the preparation process of the method can improve the experimental safety;
the etched two-dimensional titanium carbide is obtained by cleaning with distilled water and centrifuging and collecting, and the aluminum which needs to be etched in the experiment is the generated soluble [ AlF ]6]3-Washing to obtain pure two-dimensional titanium carbide with an organ structure, so that when electrons are uniformly distributed on the surface of the two-dimensional titanium carbide, lithium ions can smoothly pass through the organ gaps, and the conductivity of the electrolyte is increased;
and the method is characterized in that when the modified polymer electrolyte is assembled, the modified interface is contacted with a lithium sheet, the combined compatibility of the two-dimensional titanium carbide conducting electrons in the modified layer and the acetylene black is equivalent to the series connection of an equivalent resistor between an electrode and the electrolyte interface, the uniform distribution of electrons is promoted, the numerical value of the equivalent resistor is equivalent to the polarizability, the current density passing through a negative electrode close to the positive electrode is high, the polarization value of the negative electrode is also high, the voltage drop caused by polarization is also large, the actual current density at each position on the whole negative electrode surface tends to be uniform, so that a uniform lithium deposition layer is obtained, the uniform deposition capability can be improved by improving the polarizability of the negative electrode, the current density of lithium ion deposition is the same, and the lithium ion deposition is induced to be uniform, suppressing the generation of lithium dendrites. On the other hand, the combined compatibility of the two-dimensional titanium carbide and the acetylene black can promote the dense and efficient formation of a Solid Electrolyte Interface (SEI) film, and due to the inherent fluorine termination in the two-dimensional titanium carbide, the two-dimensional titanium carbide can react with lithium ions in the initial lithiation process and form the lithium fluoride-containing solid electrolyte interface film in situ between a polymer electrolyte and a lithium anode interface.
Compared with the prior art, the invention effectively reduces the bulk impedance and the interface impedance of the polymer electrolyte, so that a stable and compact solid electrolyte interface film is formed between the polymer electrolyte and the lithium anode, the problems of the formation of lithium dendrite on the cycle performance and the safety performance of the battery are prevented, and the charge/discharge specific capacity and the capacity retention rate of the all-solid-state lithium ion battery are improved.
Drawings
In order to more clearly illustrate the modification results of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below;
FIG. 1 is a graph of bulk impedance of a comparative example membrane of the present invention;
FIG. 2 is a graph of bulk impedance of a membrane for a method of modifying an all solid-state lithium ion battery interface with two-dimensional titanium carbide-acetylene black;
FIG. 3 is a graph of conductivity versus temperature for comparative example membranes of the invention;
FIG. 4 is a graph of the conductivity of a membrane as a function of temperature for a method of modifying an all solid-state lithium ion battery interface with two-dimensional titanium carbide-acetylene black;
FIG. 5 is a graph of specific capacity versus efficiency for comparative examples of the present invention;
fig. 6 is a specific capacity-efficiency graph of a method of modifying an all solid-state lithium ion battery interface with two-dimensional titanium carbide-acetylene black;
FIG. 7 is a graph of capacity versus voltage for a comparative example of the present invention;
fig. 8 is a capacity-voltage diagram of a modification method of an all solid-state lithium ion battery interface using two-dimensional titanium carbide-acetylene black;
FIG. 9 is a magnification view of a comparative example of the present invention;
fig. 10 is a magnification diagram of a modification method of an interface of an all solid-state lithium ion battery using two-dimensional titanium carbide-acetylene black;
FIG. 11 is a graph of impedance versus days of symmetric cell placement for comparative examples of the invention;
fig. 12 is a diagram of impedance of symmetric battery days of rest for a method of modifying an all solid-state lithium ion battery interface with two-dimensional titanium carbide-acetylene black;
FIG. 13 is a graph of interfacial resistance versus temperature for a comparative example of the present invention;
fig. 14 is a graph of the change of interface impedance with temperature of a method of modifying an interface of an all solid-state lithium ion battery with two-dimensional titanium carbide-acetylene black;
FIG. 15 is a constant current polarization diagram of a comparative example of the present invention;
fig. 16 is a constant current polarization diagram of a method for modifying an all solid-state lithium ion battery interface with two-dimensional titanium carbide-acetylene black;
FIG. 17 is an SEM image of the surface of a lithium plate after 50 cycles of the lithium iron phosphate half-cell of the comparative example of the invention;
fig. 18 is a SEM image of the surface of a lithium sheet after 50 cycles of lithium iron phosphate half-cell cycle by a method of modifying an interface of an all-solid-state lithium ion battery with two-dimensional titanium carbide-acetylene black;
FIG. 19 is an SEM image of the surface of a lithium sheet after a lithium iron phosphate half-cell of a comparative example of the present invention is left to stand at 40 ℃ for 10 hours;
FIG. 20 is an SEM image of the surface of a lithium sheet after a lithium iron phosphate half-cell is kept stand for 10 hours at 40 ℃ by a method for modifying an interface of an all-solid-state lithium ion battery by using two-dimensional titanium carbide-acetylene black;
FIG. 21 is a N1s diagram of modified layer XPS of comparative example of the present invention;
fig. 22 is a N1s diagram of a modification layer XPS of a modification method of an all solid-state lithium ion battery interface using two-dimensional titanium carbide-acetylene black;
FIG. 23 is a F1s plot of modified layer XPS of comparative example of the present invention;
fig. 24 is a F1s diagram of a modified layer XPS in a method of modifying an all solid-state lithium ion battery interface with two-dimensional titanium carbide-acetylene black.
Detailed Description
The present invention is described in further detail below with reference to examples, but the subject matter of the present invention is not limited to the following examples, and any technologies realized based on the above contents of the present invention fall within the scope of the present invention.
Experimental medicine
Experimental equipment
Comparative example 1
0.1g of acetylene black solid powder is weighed in a weighing bottle, evenly mixed with polymer electrolyte precursor slurry according to the mass ratio of 2:5, and dropwise added with N-methyl pyrrolidone to adjust to proper concentration. The surface of the polymer electrolyte film was coated with a 50 μm thick film by doctor blade, and dried in an oven at 100 ℃. And assembling the prepared polymer electrolyte into a lithium iron phosphate half-cell.
Example 1
Weighing two-dimensional titanium carbide and acetylene black powder in a mass ratio of 1:1 in a weighing bottle, adding polymer electrolyte precursor solution and NMP, and uniformly mixing. And preparing a two-dimensional titanium carbide modified layer on the surface of the polymer electrolyte by adopting a blade coating method. And assembling the prepared polymer electrolyte into a lithium iron phosphate half-cell.
Wherein the mass ratio of the solid powder to the polymer electrolyte precursor liquid in the modified layer slurry, and the blade coating and baking methods of the modified polymer electrolyte were exactly the same as those in comparative example 1.
Performance characterization of the above examples and comparative examples
1) And (4) measuring impedance. The resistance of the polymer electrolyte is an important standard for measuring the performance of the polymer electrolyte, and has important influence on the charge and discharge performance of the battery. The resistance of the polymer electrolyte is tested by adopting an electrochemical alternating current impedance spectrum, the instrument model is CHI760E type electrochemical workstation of Shanghai Chenghua, the frequency is 0.01-100000Hz, the polymer electrolyte is dried before testing, and a stainless steel symmetrical blocking battery is assembled by taking a stainless Steel Sheet (SS) as an inert electrode for testing.
2) And (5) testing charge and discharge. A plurality of important parameters of the battery in the circulating process, such as charging and discharging specific capacity, charging and discharging efficiency, a voltage platform and the like, are obtained through a charging and discharging test of the battery, the model of the device is LAND battery test system CT2001A, the voltage is set to be 2.6V-4.0V, the current multiplying power is 0.5C, and the polymer electrolyte is assembled into the lithium iron phosphate half battery for testing.
3) And (5) testing interface impedance. And testing the interface impedance of the polymer electrolyte film and the electrode by adopting an electrochemical impedance spectrum so as to judge the effect of the modified layer on the stability of the electrolyte-electrode interface, wherein the model of an electrochemical workstation is CHI760E, the frequency is 0.01-100000Hz, and the lithium iron phosphate half-cell is assembled and placed for different days for testing.
4) And (5) constant current polarization test. Testing the interface stability of the polymer electrolyte and the electrode by a constant current polarization method, performing constant current charging and discharging on the polymer battery by using constant current density, and judging the quality degree of the interface action of the polymer electrolyte surface modification layer and the lithium electrode by using a voltage-time curve, wherein the instrument model is a LAND battery testing system CT2001A, and the current density is 0.05 mA-cm-2The battery assembly mode is a lithium symmetrical battery.
5) Scanning Electron Microscope (SEM) testing. And observing the surface appearance of the lithium sheet by adopting a Scanning Electron Microscope (SEM), wherein the model of the device is FEI silicon 200, the accelerating voltage is 0.2-30kV, the resolution is 20kV, drying the prepared sample, putting the sample into liquid nitrogen for quenching, and adhering the obtained sample on a sample rack coated with conductive adhesive for testing.
6) X-ray photoelectron spectroscopy (XPS) test. The method comprises the steps of analyzing the components of an interface passivation layer (SEI) of a polymer electrolyte and a lithium electrode through an XPS test, observing component changes of solid electrolyte interface films and chemical states of elements generated under different polymer electrolytes and different circulation states, wherein the model of the device is Thermo Fisher ESCALAB Xi +, the test parameters are aluminum/magnesium targets (h v is 1486.6eV), the high resolution energy flux is 30eV, the step length is 0.05eV, the standard peak of C1s is 285eV, a half cell is disassembled before the test, one side of the polymer electrolyte, which is in contact with a lithium sheet, is used as a test surface, and experimental data are fitted through XPAK SPE 41.
FIG. 1 is a graph of bulk impedance of comparative example films of the present invention. The impedance of the polymer electrolyte is around 35 Ω.
Fig. 2 is a bulk impedance diagram of a membrane using a two-dimensional titanium carbide-acetylene black modification method for an all solid-state lithium ion battery interface. The resistance of the polymer electrolyte after the two-dimensional titanium carbide-acetylene black modification is about 10 omega. The results show that the interfacial layer of two-dimensional titanium carbide-acetylene black can make the surface of the polymer electrolyte more flat and the contact with the lithium anode more tight.
Fig. 3 is a graph of conductivity versus temperature for comparative example membranes of the invention. The temperature of the material is linearly changed above 105 ℃, and the material meets the Arrhenius equation. By the formula sigma ═ sigma0exp(-EaCalculated as/RT), the activation energy of the polymer electrolyte was 8.43 kJ. mol-1。
Fig. 4 is a graph of the change in conductivity of a membrane with temperature using a two-dimensional titanium carbide-acetylene black modification method for an all solid-state lithium ion battery interface. The polymer electrolyte is nonlinear within the temperature range of 25-105 ℃ and linearly changes above 105 ℃, and the activation energy of the polymer electrolyte modified by the two-dimensional titanium carbide-acetylene black is 6.90 kJ.mol-1The two-dimensional titanium carbide-acetylene black modified layer is shown to enhance the migration of lithium ions.
FIG. 5 is a graph of specific capacity versus efficiency for comparative examples of the present invention. The initial discharge capacity of the polymer electrolyte at 0.2C and 0.5C was 100mAh g-1After 50 times of circulation, the solution decays to 66mAh g-1The capacity fade is faster.
Fig. 6 is a specific capacity-efficiency diagram of a method for modifying an all-solid-state lithium ion battery interface with two-dimensional titanium carbide-acetylene black. The initial specific discharge capacity of the modified polymer electrolyte at 0.2C and 0.5C is 111.8 mAh.g-1After 50 cycles, the ratio is still 99.5mAh g-1The attenuation amplitude is smaller.
FIG. 7 is a graph of capacity versus voltage for comparative examples of the present invention. The charge and discharge plateaus of the battery become shorter and shorter from the 1 st cycle of the polymer electrolyte to the end of the 50 th cycle. It shows that the redox reaction equilibrium of the cathode and the anode is destroyed and the polarization phenomenon is severe during the battery cycling process.
Fig. 8 is a capacity-voltage diagram of a modification method of an all solid-state lithium ion battery interface using two-dimensional titanium carbide-acetylene black. In 50 cycles, the charge and discharge platform has no obvious change, and the potential difference of the charge and discharge platform of the modified polymer electrolyte is 0.24V, which is reduced by 0.06V compared with 0.3V of the original polymer electrolyte, so that the modified layer effectively inhibits the occurrence of polarization, and the potential difference of the polymer electrolyte is obviously reduced.
FIG. 9 is a magnification chart of a comparative example of the present invention. The discharge specific capacity of the original polymer electrolyte lithium iron phosphate half battery is 117 mAh.g when the lithium iron phosphate half battery is circulated under the multiplying power of 0.1C, 0.2C, 0.5C, 1C and 0.2C-1、102mAh·g-1、75mAh·g-1、35mAh·g-1And 102 mAh. g-1。
Fig. 10 is a magnification chart of a method for modifying an interface of an all solid-state lithium ion battery with two-dimensional titanium carbide-acetylene black. The discharge specific capacities of the two-dimensional titanium carbide-acetylene black modified polymer electrolyte under the same multiplying power during circulation are respectively 147mAh g-1、142.1·mAh g-1、126.4mAh·g-1、106.8mAh·g-1And 142.9mAh · g-1And the cycling stability of the battery is obviously improved.
Fig. 11 is a plot of day impedance for a symmetrical cell of a comparative example of the present invention. Membrane resistance (R) of the original polymer electrolyte lithium iron phosphate half-cell after standing for 1, 5 and 10 daysf) 53.69 Ω, 59.71 Ω and 47.07 Ω, respectively.
Fig. 12 is a symmetrical battery standing day impedance diagram of a method for modifying an all-solid-state lithium ion battery interface with two-dimensional titanium carbide-acetylene black. Membrane resistance (R) of the original polymer electrolyte lithium iron phosphate half-cell after standing for 1, 5 and 10 daysf) 18.61 omega, 19.45 omega and 20.78 omega respectively, which are much smaller than the two-dimensional titanium carbide-acetylene black before modification. This indicates that the occurrence of interfacial side reactions is suppressed by the modified layer. The lithium ions are induced to be uniformly deposited, so that the interface impedance can be effectively reduced, and the interface stability is improved.
FIG. 13 is a graph showing the interfacial resistance with temperature of comparative examples of the present invention. The activation energy of the solid electrolyte interfacial film before modification was 67.77 kJ. mol according to the Arrhenius equation-1。
Fig. 14 is a graph showing the change of interface impedance with temperature in a method of modifying an interface of an all-solid lithium ion battery with two-dimensional titanium carbide-acetylene black. As shown in the figure, the interfacial resistance decreased with an increase in temperature, and no inflection point appeared, indicating that the interfacial film of the solid electrolyte was producedThe conductive behavior does not change with changes in temperature. The activation energy of the modified solid electrolyte interfacial film is 9.32 kJ.mol by combining with the Arrhenius equation-1The activation energy after modification is reduced, which indicates that the presence of two-dimensional titanium carbide and acetylene black is easier to reduce the side reaction at the interface and form a stable SEI film.
FIG. 15 is a constant current polarization diagram of a comparative example of the present invention. The assembled symmetrical cell fluctuated with cycles, and the polarization voltage was 0.18V.
Fig. 16 is a constant current polarization diagram of a method for modifying an interface of an all solid-state lithium ion battery using two-dimensional titanium carbide-acetylene black. The symmetrical cell assembled with the modified polymer electrolyte remained stable during 100h of cycling, and the polarization voltage (0.04V) was also significantly lower than that of the comparative example. Further proves that the two-dimensional titanium carbide-acetylene black coating can effectively reduce the interface impedance of the polymer electrolyte and reduce the polarization phenomenon, thereby ensuring that the cycle performance of the battery is better.
Fig. 17 is an SEM image of the surface of a lithium sheet after 50 cycles of the lithium iron phosphate half-cell of the comparative example of the present invention. The growth of lithium dendrites is a key factor in measuring the effect of the modified coating on the modification of the polymer electrolyte and electrode interface. The characterization result of 50 cycles of the original polymer electrolyte lithium iron phosphate half-cell shows that the dendritic crystal on the surface of the lithium sheet is not obviously increased along with the increase of the cycle number, but the growth of the dendritic crystal is not uniform.
Fig. 18 is an SEM image of the surface of a lithium sheet after 50 cycles of lithium iron phosphate half-cell cycling using a method for modifying an interface of an all-solid-state lithium ion battery with two-dimensional titanium carbide-acetylene black. After 50 cycles, the lithium iron phosphate half-cell with the polymer electrolyte modified by the two-dimensional titanium carbide-acetylene black has no large and prominent dendritic crystal on the surface of the lithium sheet, and the dendritic crystal is uniformly distributed. This indicates that lithium dendrite growth still remains on the surface of the lithium sheet after the two-dimensional titanium carbide-acetylene black is modified. But the dendrites are uniformly distributed, are more smooth and dense, cannot pierce the film to cause short circuit, and can solve the problem of the aggregation and growth of the dendrites of lithium in the lithium ion battery. Fig. 19 and 20 are SEM images of the surface of the lithium plate after the original polymer electrolyte lithium iron phosphate half-cell and the two-dimensional titanium carbide-acetylene black modified polymer electrolyte lithium iron phosphate half-cell are left standing at 40 ℃ for 10 hours, respectively. Lithium ion deposition of the lithium iron phosphate half-cell assembled by the original polymer electrolyte is uneven and is distributed on the surface of a lithium sheet in a moss shape or a tree shape. During cycling, lithium ions tend to accumulate on the dendritic surface formed due to the tip effect. With the increase of the deposition amount, the lithium dendrite grows seriously and easily pierces the film, causing a safety problem. And SEI films on the surfaces of lithium iron phosphate half-batteries assembled by the polymer electrolyte prepared by modifying the two-dimensional titanium carbide-acetylene black are uniformly distributed and are spherical. According to the studies by Shi et al, these spherical solid electrolyte interface membranes are hollow structures and will be captured by the spherical solid electrolyte interface membranes during the formation of lithium dendrites without causing lithium deposition. The combination of charge and discharge performance shows that the interface layer modified by the two-dimensional titanium carbide-acetylene black can perfectly solve the growth problem of lithium dendrites and has good electrode/electrolyte interface compatibility.
FIG. 21 is a N1s diagram of modified layer XPS of comparative example of the present invention.
Fig. 22 is a N1s diagram of a modified layer XPS in a method of modifying an all solid-state lithium ion battery interface with two-dimensional titanium carbide-acetylene black. Unlike the comparative example, lithium nitride (Li) was found in the solid electrolyte interface film formed after modification of two-dimensional titanium carbide-acetylene black3N) peak. Lithium nitride is one of the fastest lithium ion conductors and has an ionic conductivity of 10 at room temperature3～104S·cm-1. It can effectively improve the lithium ion transmission capability of the solid electrolyte interface film and relieve the lithium ion concentration gradient on the surface of the cathode.
FIG. 23 is a F1s plot of modified layer XPS of comparative example of the present invention;
fig. 24 is a F1s diagram of a modified layer XPS in a method of modifying an all solid-state lithium ion battery interface with two-dimensional titanium carbide-acetylene black. The existence of the two-dimensional titanium carbide can promote the formation of lithium fluoride, a compact and stable solid electrolyte interface film is formed between a polymer electrolyte and a lithium anode interface, and in the existence of the lithium fluoride, the metal lithium tends to grow horizontally on the two-dimensional titanium carbide, so that the deposition of spherical lithium is promoted, and the safety problem of the battery in the circulating process is guaranteed.
Claims (6)
1. A method for modifying an all-solid-state lithium ion battery interface by using two-dimensional titanium carbide-acetylene black is characterized by comprising the following specific steps: uniformly mixing two-dimensional titanium carbide and acetylene black, adding a polymer electrolyte precursor solution, adding an organic solvent, uniformly stirring, preparing a modified coating on the surface of the polymer electrolyte by adopting a blade coating method, and drying in an oven to obtain a polymer electrolyte with a two-dimensional titanium carbide and acetylene black modified interface layer;
the mass ratio of the two-dimensional titanium carbide to the acetylene black is 1-4: 1-4;
the mass ratio of the two-dimensional titanium carbide and acetylene black mixed solid to the polymer electrolyte precursor liquid is 1-5: 5;
the organic solvent is one or more of N-methyl pyrrolidone, N, N-dimethylformamide or N, N-dimethylacetamide.
2. The method for modifying the interface of the all-solid-state lithium ion battery by using the two-dimensional titanium carbide-acetylene black as claimed in claim 1, wherein the organic solvent is dropwise added at a speed of 20 drops/min, and the stirring time is 8-14 h.
3. The method for modifying the interface of the all-solid-state lithium ion battery by using the two-dimensional titanium carbide-acetylene black as claimed in claim 1, wherein the thickness of the modified coating is 10-50 μm.
4. The method as claimed in claim 1, wherein the vacuum drying temperature is 100-120 ℃.
5. The method for modifying the interface of the all-solid-state lithium ion battery by using the two-dimensional titanium carbide-acetylene black as claimed in claim 1, wherein the two-dimensional titanium carbide is obtained by etching titanium aluminum carbide by hydrofluoric acid, the hydrofluoric acid is obtained by lithium fluoride and hydrochloric acid, and the etched two-dimensional titanium carbide is obtained by cleaning with distilled water and centrifuging and collecting.
6. The method for modifying the interface of the all-solid-state lithium ion battery by using the two-dimensional titanium carbide-acetylene black as claimed in claim 1, wherein the modified polymer electrolyte is in contact with a lithium sheet when the battery is assembled.
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| JP2011195864A (en) * | 2010-03-18 | 2011-10-06 | Katsuyoshi Kondo | Titanium based composite material, and method for producing the same |
| CN103682287A (en) * | 2013-12-19 | 2014-03-26 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon-based composite anode material, preparation method thereof and battery |
| CN112593134A (en) * | 2020-11-25 | 2021-04-02 | 燕山大学 | Niobium-doped two-dimensional layered titanium carbide composite material and preparation method and application thereof |
| CN112768758A (en) * | 2021-01-27 | 2021-05-07 | 桑顿新能源科技有限公司 | Solid electrolyte, preparation method thereof, all-solid-state lithium ion battery and manufacturing method thereof |
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| JP2011195864A (en) * | 2010-03-18 | 2011-10-06 | Katsuyoshi Kondo | Titanium based composite material, and method for producing the same |
| CN103682287A (en) * | 2013-12-19 | 2014-03-26 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery silicon-based composite anode material, preparation method thereof and battery |
| CN112593134A (en) * | 2020-11-25 | 2021-04-02 | 燕山大学 | Niobium-doped two-dimensional layered titanium carbide composite material and preparation method and application thereof |
| CN112768758A (en) * | 2021-01-27 | 2021-05-07 | 桑顿新能源科技有限公司 | Solid electrolyte, preparation method thereof, all-solid-state lithium ion battery and manufacturing method thereof |
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