CN111987348A - Preparation method of NASICON type solid-state battery - Google Patents
Preparation method of NASICON type solid-state battery Download PDFInfo
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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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
- H01M10/058—Construction or manufacture
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to the technical field of solid-state batteries, and particularly provides a preparation method of a NASICON type solid-state battery for solving the problem of the existing NASICON solid-state electrolyte (LiTi)2PO4) There are a number of problems, and interfacial contact problems in solid-state batteries. Firstly, modifying an LTP matrix by using trivalent cations to obtain a solid electrolyte Li1.3M0.3Ti1.7(PO4)3The electrolyte improves the ionic conductivity of the solid electrolyte and reduces the side reaction of Li metal and the electrolyte; secondly, a small amount of LFTP or LCTP is introduced into the traditional lithium iron phosphate anode, and the coating process is matched and improved, so that the interface contact between the anode and an electrolyte is effectively improved; finally, when assembling the solid-state battery, lithium hexafluorophosphate is dripped on the upper surface of the electrolyte layer to infiltrate the interface, and an excessive interface is constructed(ii) a The final preparation can obtain a kind of total [ PO ]4]3‑The solid-state battery with the framework, namely the phosphate anode, the phosphate electrolyte and the phosphate transition interface, greatly prolongs the cycle life of the solid-state battery.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly provides a preparation method of a NASICON type solid-state battery.
Background
Lithium Ion batteries (abbreviated as LIB), also called Lithium batteries, are also called rocking chair batteries because Li ions shuttle back and forth continuously during the charging and discharging process of the batteries. Commercial lithium ion batteries were developed by sony from the 1800 year of Volta invention batteries to 1991, during which lead acid batteries, iron-nickel batteries, nickel-cadmium batteries and nickel-hydrogen batteries were experienced. The lithium ion battery is an epoch-making invention, has the characteristics of high efficiency, long service life, low relative pollution hazard, quick charging and the like, is the battery with the most perfect performance in all secondary chemical power supplies used commercially so far, and is a great factor for promoting the high-speed development of new energy electric vehicles.
At present, most of common lithium ion batteries are liquid batteries, namely, a mode of a positive electrode, a liquid electrolyte, a diaphragm and a negative electrode. In the first half of 2020, more than 90 million global new energy automobile passenger cars are available, and under the large background of high-speed development of the new energy automobile market, the traditional mode no longer meets the higher development requirements of new energy automobiles, on one hand, because the electrolyte occupies a large volume space, in addition, the liquid diaphragm generates local heavy current after the growth of the lithium dendrite and is easy to puncture short circuit, meanwhile, the electrolyte can generate a large amount of heat, the cost of a cooling system is increased in an automobile power system, but the most critical is the safety problem, and the battery is overheated due to overcharge, impact, short circuit, water soaking and the like, and related researches show that, the SEI film is decomposed at 90-120 ℃, the electrolyte negative electrode is reacted at a temperature higher than 120 ℃ to generate a large amount of combustible gas, the diaphragm is melted at 130 ℃ to generate internal short circuit, the electrolyte at 140 ℃ is evaporated, and the positive electrode at a temperature higher than 200 ℃ is decomposed to release gas. Meanwhile, the liquid state also faces the problems of dissolution of excessively low metal of the anode, oxygen evolution of the anode, dry consumption of electrolyte, corrosion of aluminum foil and the like, which are important causes of thermal runaway of the power battery, and by taking 2019, 5-8 months as an example, a report on the national supervision platform big data safety supervision result of a new energy automobile shows that 79 major safety events of the new energy automobile occur altogether, and the research of the anode material focuses on improving the structural stability and energy density of the anode, and the diaphragm modification is slow, so that the method has certain limitations.
In order to fundamentally solve the safety problem, research on solid-state batteries is widely conducted worldwide; compared with commercial lithium ion batteries, the most outstanding advantage of all-solid-state batteries is safety; its main advantage lies in: the solid-state battery can bear higher voltage due to the absence of electrolyte voltage decomposition and high-voltage-resistant energy difference of the diaphragm; compared with the electrolyte, the solid electrolyte is not easy to continuously generate side reaction with lithium, and the dissolution of transition metal ions does not exist; the solid-state battery has the advantages of non-combustibility and corrosion resistance, and greatly reduces the possibility of thermal runaway and combustion fire. Currently, research on solid-state batteries mainly focuses on modification research of solid electrolytes and development of novel electrolytes; on the other hand, studies on reduction in resistance by interfacial contact between positive and negative electrodes have been focused. Common solid electrolytes are substantially sulfide-based solid electrolytes, such as Li10GeP2S12Oxide-based solid electrolytes such as olive-structured solid electrolytes represented by Lithium Lanthanum Zirconium Oxide (LLZO), organic polymers such as polyethylene oxide PEO, and the like, and NASICON-based solid electrolytes. Among these solid electrolytes, NASICON type solid electrolytes have high conductivity, stable water and oxygen, and good performanceThermal and mechanical stability, and various kinds of advantages which are convenient for research, thereby having great application prospect; however, the existing NASICON solid electrolyte LiTi2PO4The method has the problems of low conductivity, low ionic conductivity especially at low temperature, side reaction of lithium metal and Ti, and the like.
Disclosure of Invention
The object of the present invention is to address the above-mentioned prior NASICON solid electrolyte (LiTi)2PO4) The problems existing and the problem of interface contact in the solid-state battery, and provides a preparation method of the NASICON type solid-state battery; on one hand, a trivalent cation is adopted to modify the NASICON type solid electrolyte to obtain the solid electrolyte Li1.3M0.3Ti1.7(PO4)3And M ═ Fe and Cr (abbreviated as LFTP and LCTP, respectively), and a solid electrolyte composite slurry is prepared therefrom; on the other hand, a small amount of LFTP or LCTP is introduced into the traditional lithium iron phosphate anode to prepare anode slurry matched with the solid electrolyte composite slurry; finally, coating the anode slurry on the upper surface of the aluminum foil, and coating the solid electrolyte composite slurry on the anode sheet under the condition that the anode slurry is not completely dried so as to obtain an anode electrolyte interface with good contact; the cycle life of the finally prepared NASICON solid-state battery is greatly prolonged.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a NASICON type solid-state battery comprises the following steps:
and 4, adding lithium iron phosphate, conductive carbon black, PVDF, LATP or LCTP into an NMP solvent, mixing and stirring for 5-15 hours to obtain lithium iron phosphate anode slurry, wherein the weight ratio of lithium iron phosphate: conductive carbon black: PVDF: the mass ratio of LFTP/LCTP is as follows: 80:10:5:5, and the dosage of NMP solvent is as follows: each 0.5g of solute was dispersed in 1ml of NMP solvent;
and 7, taking the metal lithium as a negative electrode, covering the negative electrode on the upper surface of the electrolyte layer in an Ar atmosphere, and assembling to obtain the solid-state battery.
Further, the step 7 further includes an infiltration process, specifically: dripping 1-10 μ L lithium hexafluorophosphate on the upper surface of the electrolyte layer, and soaking for 5-30 min.
The invention has the beneficial effects that:
the invention provides a method for preparing a NASICON type solid-state battery,
first, a trivalent cation (Fe) is used3+、Cr3+) Modifying LTP to obtain solid electrolyte Li1.3M0.3Ti1.7(PO4)3Fe and Cr (LFTP and LCTP); trivalent cation (Fe)3+、Cr3+) Compensating lithium ions are introduced to partially replace the LTP matrix to offset lost positive charges, so that enhanced ionic conductivity is obtained, and the ionic conductivity of the electrolyte at low temperature can be effectively improved; and valence-changed Fe3+、Cr3+Ions sacrifice the extra-nuclear electron orbit to a certain extent to accept free electrons from lithium metal and indirectly support Ti4+The lithium ion battery is not reduced by Li metal, so that the side reaction of the Li metal and the solid electrolyte is effectively reduced, and the cycle life of the solid battery is prolonged;
secondly, preparing the solid electrolyte composite slurry based on the modified LFTP and LCTP electrolytes; meanwhile, a small amount of LFTP/LCTP solid electrolyte is introduced into the traditional lithium iron phosphate anode, so that the anode and the electrolyte have better cooperativity, and the polarization degree is reduced; in addition, in order to further ensure that the interface contact between the anode and the electrolyte is good, the coating process of the anode and the electrolyte is improved, namely, under the condition that the drying and evaporation of the anode are not thorough, the solid electrolyte slurry is directly coated on the anode by a four-side preparation device in a scraping way; the improvement of the interface contact between the positive electrode and the electrolyte can further prolong the cycle life of the solid-state battery;
finally, when the solid-state battery is assembled, a very small amount (5 mu L) of lithium hexafluorophosphate is dripped on the upper surface of the electrolyte layer to infiltrate an interface, a transition interface is constructed, and then the assembly is carried out;
in conclusion, the preparation method of the invention can obtain the total [ PO ]4]3-A skeletal solid-state battery, namely a phosphate positive electrode, a phosphate electrolyte, and a phosphate transition interface; the cycle life of the solid-state battery can be greatly prolonged, and a feasible scheme is provided for the comprehensive commercialization of the solid-state battery.
Drawings
FIG. 1 is a process flow diagram of a method for manufacturing a NASICON type solid-state battery according to the present invention.
FIG. 2 shows XRD patterns (a) of LFTP and LCTP electrolytes, SEM patterns (b-c) of coated electrode interfaces, Mapping patterns (LFTP (d-g) and LCTP (h-k)) of interface layers, and TEM patterns (LFTP (l-m) and LCTP (n-o)) of LFTP and LCTP electrolytes in examples of the present invention.
FIG. 3 is an XPS spectrum of LFTP, LCTP electrolytes described in the examples of the present invention.
FIG. 4 shows the ion conductivity diagram (a) and LSV diagram (b) of LFTP and LCTP electrolytes, and the step current charging and discharging curves (c-d) of lithium symmetrical batteries in the examples of the present invention.
Fig. 5 is a graph showing the charge-discharge curves (lftp (a), lctp (b)), rate cycle graph (c), and cycle performance graph (d) of the solid-state battery according to the embodiment of the present invention.
Fig. 6 is an EIS spectrum of the electrolyte membrane according to the example of the present invention.
FIG. 7 is a graph showing a comparison of ion conductivities at different temperatures in examples of the present invention.
FIG. 8 is an Arrhenius diagram of LFTP and LCTP electrolytes in an embodiment of the present invention.
FIG. 9 is a graph showing the combustion stability of the electrolyte membrane LFTP (a), LCTP (b) in the example of the present invention.
FIG. 10 is a comparison graph of water stability of the electrolyte membrane in the example of the present invention, initial (a), 10days (b).
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings.
The embodiment provides a method for preparing a NASICON-type solid-state battery, the process flow of which is shown in fig. 1, and the method specifically comprises the following steps:
and 4, adding lithium iron phosphate, conductive carbon black, PVDF, LATP or LCTP) into an NMP solvent, mixing and stirring for 5-15 hours to obtain lithium iron phosphate anode slurry, wherein the weight ratio of lithium iron phosphate: conductive carbon black: PVDF: the mass ratio of LFTP/LCTP is as follows: 80:10:5:5, and the dosage of NMP solvent is as follows: each 0.5g of solute was dispersed in 1ml of NMP solvent;
step 7, the electrolyte slurry obtained in the step 3 is scraped and coated on a glass plate by adopting a four-side preparation device, and a film is formed after vacuum thermal evaporation; and assembling the cut electrolyte membrane with a Li symmetrical battery, then using a stainless steel sheet to make a blocking electrode to measure alternating current impedance, and calculating the ionic conductivity.
The test results of this example are illustrated below with reference to the accompanying drawings:
the invention adopts trivalent cation to modify LiTi2PO4The matrix is shown as an XRD pattern (a) in figure 2, and the result shows that the phase is consistent with that of a standard card and the crystallinity is good; as shown in the SEM image, Mapping image, TEM image and HRTEM image in fig. 2, the thickness of the positive electrode layer is about 50 μm, the thickness of the electrolyte layer is about 50 μm, the two interfaces are tightly bonded, and no obvious gap is present, which effectively illustrates the advantages of the solid-state battery assembly process of the present invention, i.e., the solid-state electrolyte is infiltrated into the positive electrode, and the infiltration of a very small amount of electrolyte promotes the good overall contact of the solid-state battery system, thereby greatly improving the cycle performance of the solid-state battery.
FIG. 3 shows XPS spectra of LFTP and LCTP electrolytes, which indicates the element content and oxidation valence state in LFTP and LCTP powders, and the peak position corresponds well; calcination of the precursor in air has only a very small amount of Ti4+Is reduced to Ti3+The valence state of the atomic structure in the powder is stable; at the same time, LFTP, LCTP electrolytes also have a wide electrochemical stability window, as shown by the LSV plot in FIG. 4, relative to Li/Li+4.619V and 4.481V respectively, and further, the charge-discharge curves of the lithium symmetric battery as shown in FIG. 4 also show that the electrolyte prepared by the design slurry of the invention has good Li ion shuttling performance and the polarization voltage is lower than 0.05V.
An assembled LiFePO employing LFTP electrolyte is shown in FIG. 54Li solid-state battery capable of providing up to 139.7mAh g at 0.1C and 25 deg.C-1And a battery using an LCTP electrolyte can provide 133.2 mAh-g-1The discharge specific capacity of the composite material shows excellent rate discharge performance and cycling stability.
FIG. 6 shows EIS spectra of LFTP and LCTP electrolyte membranes, and the calculated ion conductivities at different temperatures are compared with those of FIG. 7, so that the LFTP and LCTP solid electrolytes obtained in this example have satisfactory ion conductivities at room temperature, respectively of 0.147 mS cm and 0.181mS cm-1And especially exhibits higher ionic conductivity at low temperatures (-5 ℃) than conventional LATP solid-state electrolytes; meanwhile, as can be seen from the Arrhenius graph in fig. 8, the linear consistency of the ion conductivity of the LFTP and LCTP electrolytes is also good with the temperature change.
As shown in fig. 9 and 10, which are comparative graphs of the combustion stability and the water stability of the electrolyte membrane of the present embodiment, respectively, the results show that the electrolyte of the present invention has good water stability and combustion resistance.
In conclusion, based on the LFTP and LCTP electrolytes and the assembly preparation process matched with the LFTP and LCTP electrolytes, the NASICON solid electrolyte (LiTi) in the prior art can be well solved2PO4) The problems existing in the prior art and the problem of interface contact in the solid-state battery provide a reference scheme for the comprehensive commercialization of the solid-state battery.
While the invention has been described with reference to specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.
Claims (2)
1. A preparation method of a NASICON type solid-state battery comprises the following steps:
step 1, using ferric nitrate or chromic nitrate and tetrabutyl titanate (C)16H36O4Ti), anhydrous lithium acetate (CH)3COOLi), ammonium dihydrogen phosphate (NH)4H2PO4) The raw materials are accurately weighed according to the stoichiometric ratio of Li to Fe/Cr to Ti to P of 1.3 to 0.3 to 1.7 to 3, tetrabutyl titanate is firstly dispersed in absolute ethyl alcohol to obtain solution A, and then anhydrous lithium acetate, ferric nitrate or chromium nitrate and phosphoric acid are addedDissolving ammonium hydrogen into deionized water to obtain solution B, dropwise adding the solution A into the solution B under stirring by using a burette, wherein the stirring speed is 1000-; then centrifugally washing the mixed sol for 3-8 times, drying at 80-125 ℃, and grinding to obtain precursor powder;
step 2, heating the precursor powder obtained in the step 1 to 650 ℃ at the heating rate of 1-5 ℃/min in a muffle furnace for presintering for 5-10h, and then heating to 700-1000 ℃ at the heating rate of 2-10 ℃/min for heat preservation for 5-10 h; naturally cooling along with the furnace, performing wet ball milling on the powder for 5-10h, and drying at 85-125 ℃ to obtain LFTP or LCTP powder;
step 3, adding the LFTP or LCTP powder obtained in the step 2 and LiTFSi into an NMP solvent, mixing and stirring for 2-5h, then adding polyvinylidene fluoride, mixing and stirring for 5-15h, and forming uniform electrolyte slurry; wherein the mass ratio of LFTP/LCTP to polyvinylidene fluoride to LiTFSi is as follows: 3:1:1, and the dosage of NMP solvent is as follows: every 0.5g of solute was dispersed in 4ml of NMP solvent;
and 4, adding lithium iron phosphate, conductive carbon black, PVDF, LATP or LCTP into an NMP solvent, mixing and stirring for 5-15 hours to obtain lithium iron phosphate anode slurry, wherein the weight ratio of lithium iron phosphate: conductive carbon black: PVDF: the mass ratio of LFTP/LCTP is as follows: 80:10:5:5, and the dosage of NMP solvent is as follows: each 0.5g of solute was dispersed in 1ml of NMP solvent;
step 5, uniformly scraping the lithium iron phosphate anode slurry obtained in the step 4 on the upper surface of an aluminum foil, and drying in an oven at 80-125 ℃ for 20-60 min to form a lithium iron phosphate anode layer;
step 6, coating the electrolyte slurry obtained in the step 3 on the upper surface of the lithium iron phosphate positive electrode layer by scraping, and drying in a drying oven at 85-125 ℃ for 12-24h to form an electrolyte layer;
and 7, taking the metal lithium as a negative electrode, covering the negative electrode on the upper surface of the electrolyte layer in an Ar atmosphere, and assembling to obtain the solid-state battery.
2. The method for preparing the NASICON-type solid-state battery according to claim 1, wherein the step 7 further comprises an infiltration process, specifically: dripping 1-10 μ L lithium hexafluorophosphate on the upper surface of the electrolyte layer, and soaking for 5-30 min.
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| CN114373884A (en) * | 2021-12-15 | 2022-04-19 | 浙江锋锂新能源科技有限公司 | Lithium metal solid-state battery with positive electrode and high safety and high cyclicity |
| CN114447421A (en) * | 2021-12-20 | 2022-05-06 | 上海空间电源研究所 | Solid electrolyte for transmitting ions through interface layer and preparation method thereof |
| CN114464808A (en) * | 2022-01-25 | 2022-05-10 | 牛墨石墨烯应用科技有限公司 | Lithium ion battery added with lithium titanium phosphate and graphene and preparation method thereof |
| CN116053401A (en) * | 2022-12-30 | 2023-05-02 | 重庆太蓝新能源有限公司 | Composite positive electrode plate, preparation method thereof and lithium battery |
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| CN114464808A (en) * | 2022-01-25 | 2022-05-10 | 牛墨石墨烯应用科技有限公司 | Lithium ion battery added with lithium titanium phosphate and graphene and preparation method thereof |
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