CN115458804A - Nano solid electrolyte lithium titanium aluminum phosphate, preparation method and application - Google Patents
Nano solid electrolyte lithium titanium aluminum phosphate, preparation method and application Download PDFInfo
- Publication number
- CN115458804A CN115458804A CN202211262306.5A CN202211262306A CN115458804A CN 115458804 A CN115458804 A CN 115458804A CN 202211262306 A CN202211262306 A CN 202211262306A CN 115458804 A CN115458804 A CN 115458804A
- Authority
- CN
- China
- Prior art keywords
- precipitate
- solid electrolyte
- lithium
- water
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a nanometer solid electrolyte lithium titanium aluminum phosphate, a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing raw materials according to the stoichiometric ratio of the lithium aluminum titanium phosphate, preparing a precipitate, and washing the precipitate; the atomic ratio of the raw materials satisfies: li: al: ti: p = (1 + x): x: (2-x): x is more than or equal to 3,0 and less than or equal to 0.5; water is used as a solvent in the process of preparing the precipitate; adding water into the washed precipitate to prepare a suspension, moving the suspension into a sealed pressure container, reacting for a period of time at a certain temperature, and drying the reacted material to obtain precursor powder; and carrying out heat treatment on the precursor powder to obtain the solid electrolyte lithium titanium aluminum phosphate. The solid electrolyte lithium titanium aluminum phosphate obtained by the invention has the D50 less than 200nm, is applied to a lithium ion battery, and can effectively improve the overall performance of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a nanometer solid electrolyte lithium titanium aluminum phosphate, a preparation method and application thereof.
Background
In the solid electrolyte, lithium aluminum titanium phosphate Li 1+x Al x Ti 2-x (PO 4 ) 3 (x = 0.3-0.5) (hereinafter referred to as "LATP") chamberThe high temperature ionic conductivity, approaching commercial electrolyte levels, is of particular concern. The conventional methods for synthesizing lithium aluminum titanium phosphate mainly comprise a solid-phase sintering method, a liquid-phase precipitation method, a sol-gel method and the like, and among the preparation methods, the solid-phase sintering method and the precipitation method have simple processes and are suitable for industrial mass production. In the prior art, the LATP powder prepared by solid phase sintering method usually has high energy, long reaction time, and is very easy to produce impurity phase, and the particle size of the powder is generally large (>10 μm); in order to obtain the LATP powder material with nanometer size, the reported data generally adopts a sol-gel method for preparation, and the preparation method generally needs to adopt some organic solvents such as ethanol, glycol and the like, which greatly limits the requirement on equipment in the process amplification process.
Disclosure of Invention
The invention provides a nanometer solid electrolyte lithium titanium aluminum phosphate, a preparation method and application thereof, which are used for solving the problems that the existing LATP solid electrolyte prepared by the prior art is large in particle size, and the synthesis temperature is too high in the preparation process, so that the lithium loss is easily caused, the energy consumption is too high, and the process is complex.
The invention provides a preparation method of nanometer solid electrolyte lithium titanium aluminum phosphate, which comprises the following steps:
step S1: preparing raw materials according to the stoichiometric ratio of the lithium aluminum titanium phosphate, preparing a precipitate by using the raw materials, and washing the precipitate; wherein, the atomic ratio of the raw materials satisfies: li: al: ti: p = (1 + x): x: (2-x): x is more than or equal to 3,0 and less than or equal to 0.5; water is used as a solvent in the process of preparing the precipitate; preferably, 0.3. Ltoreq. X.ltoreq.0.5; more preferably, x =0.3 or 0.4;
step S2: adding water into the washed precipitate to prepare a suspension, moving the suspension into a sealed pressure container, reacting for a period of time at a certain temperature, and drying the reacted material to obtain precursor powder;
and step S3: and carrying out heat treatment on the precursor powder to obtain the solid electrolyte lithium titanium aluminum phosphate.
In the scheme, the preparation method of the solid electrolyte lithium titanium aluminum phosphate adopts a water-based system, so that the equipment requirement and the environmental protection requirement in the industrial scale-up production process can be reduced. The preparation method of the invention firstly adopts water as solvent to prepare the precipitate, and washes the precipitate, and the excess ions which do not participate in the reaction in the precipitate can be removed by washing the precipitate, thereby effectively avoiding the influence of the ions on the final shape of the subsequent product. The preparation method of the invention adds water into the washed precipitate to prepare turbid liquid, then moves the turbid liquid into a sealed pressure container, reacts for a period of time at a certain temperature, can effectively control the reaction and the crystal growth, thereby leading the size of the formed initial particles to be smaller than that of the particles prepared by a common precipitation method, and further leading the precursor powder with small size. According to the invention, the small-sized precursor powder is finally subjected to heat treatment to obtain the solid electrolyte lithium titanium aluminum phosphate with the D50 smaller than 200nm, and the solid electrolyte lithium titanium aluminum phosphate is applied to the lithium ion battery, so that the overall performance of the lithium ion battery can be effectively improved.
The preparation method comprises the following steps:
step S1: adding an aluminum source, a titanium source and a phosphorus source into water to prepare a mixed salt solution; dropwise adding an alkaline solution into the mixed salt solution until the pH value is 7-10 to form the precipitate; washing the precipitate with water for 1-3 times;
step S2: uniformly mixing the washed precipitate with a lithium ion solution, adding water to prepare a suspension, transferring the suspension into a sealed pressure container, and reacting at 80-130 ℃ for 2-12 h; then drying the reacted materials to obtain precursor powder;
and step S3: and carrying out heat treatment on the precursor powder to obtain the solid electrolyte lithium titanium aluminum phosphate.
Specifically, in step S1, the alkaline solution may be selected from ammonium bicarbonate solution, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia water, and the like. The pH may be 7, 7.5, 8, 8.5, 9, 9.5, or 10, or the like, or may be other values within the above range, and is not limited herein. The number of washes may be 1, 2 or 3. In step S2, the temperature of the reaction carried into the sealed pressure vessel may be 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃, although other values within the above range are possible and are not limited thereto, and the time may be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h, and other values within the above range are also possible and are not limited thereto.
In the scheme, in order to reduce the loss of lithium in the process of preparing the precipitate, lithium salts such as lithium hydroxide, lithium nitrate, lithium acetate and the like which can be dissolved in water are mixed with the precipitate in the form of lithium ion solution and then are added into a sealed pressure container for hydrothermal reaction.
The preparation method comprises the following steps:
step S1: adding an aluminum source, a titanium source and a phosphorus source into water to prepare a mixed salt solution, and dropwise adding an alkaline solution into the mixed salt solution until the pH value is 7-10 to form a first precipitate; putting the first precipitate into water, adding lithium salt into the water, fully dispersing, and performing suction filtration to obtain a second precipitate;
step S2: adding water into the second precipitate to prepare the suspension, then transferring the suspension into a sealed pressure container, and reacting for 2-12 h at 80-130 ℃; then drying the reacted materials to obtain precursor powder;
and step S3: and carrying out heat treatment on the precursor powder to obtain the solid electrolyte lithium titanium aluminum phosphate.
Specifically, in step S1, the alkaline solution may be selected from ammonium bicarbonate solution, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia water, and the like. The pH may be 7, 7.5, 8, 8.5, 9, 9.5, or 10, or the like, or may be other values within the above range, and is not limited herein. The temperature for the reaction in the sealed pressure vessel may be 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃, or the like, or may be other values within the above range, and the reaction time is not limited thereto, and may be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h, or the like, or may be other values within the above range, and the reaction time is not limited thereto.
In the scheme, the design is carried out aiming at the lithium salt which is not soluble in water or slightly soluble in water, and in order to reduce the loss of lithium in the process of preparing the first precipitate, the lithium salt which is not soluble in water or slightly soluble in water (such as lithium carbonate) is mixed with the first precipitate in the form of lithium salt, washed and then added into the sealed pressure vessel for hydrothermal reaction.
According to the preparation method, the aluminum source comprises one or more of aluminum nitrate, aluminum chloride and aluminum hydroxide;
and/or the titanium source comprises one or more of tetrabutyl titanate and titanium tetrachloride;
and/or the phosphorus source comprises one or more of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
According to the preparation method, the lithium ion solution comprises one or more of a lithium hydroxide solution, a lithium nitrate solution and a lithium acetate solution.
According to the production method of the present invention, the lithium salt includes lithium carbonate.
According to the preparation method of the invention, the filling pressure in the sealed pressure container is maintained between 0.4MPa and 0.6MPa.
Alternatively, the filling pressure in the sealed pressure vessel may be maintained at 0.4MPa, 0.45MPa, 0.5MPa, 0.55MPa, or 0.6MPa, or the like, or may be other values within the above range, and is not limited thereto.
The filling pressure in the sealed pressure container is limited in a reasonable range, hydrothermal reaction of the precipitate can be facilitated, reaction and crystal growth can be effectively controlled, and therefore the obtained precursor powder is smaller in size and more uniform in particle distribution, and solid electrolyte lithium titanium aluminum phosphate which is small in size and uniform in particle distribution is obtained.
According to the preparation method, in the step S3, the temperature of the heat treatment is 800-950 ℃, and the time is 1-10 h.
Alternatively, in step S3, the temperature of the heat treatment may be 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃ or 950 ℃, and may be other values within the above range, which is not limited herein. The time of the heat treatment may be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, or 10h, and may be other values within the above range, which is not limited herein.
The temperature and time of the heat treatment are limited within a reasonable range, so that the internal structure of the lithium titanium aluminum phosphate crystal of the solid electrolyte can be controlled, and the obtained lithium titanium aluminum phosphate of the solid electrolyte has small size and uniform particle distribution.
The invention also provides a nano solid electrolyte lithium titanium aluminum phosphate prepared by the preparation method; the solid electrolyte lithium titanium aluminium phosphate has a D50<200nm.
The invention also provides the solid electrolyte lithium titanium aluminum phosphate prepared by the preparation method or the application of the solid electrolyte lithium titanium aluminum phosphate in a lithium ion battery.
Specifically, the solid-state electrolyte lithium titanium aluminum phosphate prepared by the preparation method or the solid-state electrolyte lithium titanium aluminum phosphate can be applied to positive and negative electrode materials added into a lithium ion battery, and a coating layer is formed on the surface of the solid-state electrolyte lithium titanium aluminum phosphate or the solid-state electrolyte lithium titanium aluminum phosphate in the process of mixing the solid-state electrolyte lithium titanium lithium phosphate with the positive and negative electrode materials, so that the thickness of the coating layer can be reduced in a nanometer size, the problem of an interface between the coating layer and the solid-state electrolyte can be improved on the basis of not influencing the battery performance of the positive and negative electrode materials, and the overall performance of the lithium ion battery can be improved.
The invention provides a nanometer solid electrolyte lithium titanium aluminum phosphate and a preparation method and application thereof. The preparation method of the invention adds water into the washed precipitate to prepare suspension, then moves the suspension into a sealed pressure container, reacts for a period of time at a certain temperature, and can effectively control the reaction and the crystal growth, thereby leading the size of the formed initial particles to be smaller than that of the particles prepared by the common precipitation method, and further leading the precursor powder with small size. According to the invention, the small-sized precursor powder is finally subjected to heat treatment to obtain the solid electrolyte lithium titanium aluminum phosphate with the D50 of less than 200nm, and the solid electrolyte lithium titanium aluminum phosphate is applied to the lithium ion battery, so that the electrical property of the lithium ion battery can be effectively improved.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or the prior art, the drawings needed for the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
Fig. 1 is an XRD spectrum of solid electrolyte LATP powder provided in example 1 of the present invention;
FIG. 2 is an SEM topography of a solid electrolyte LATP powder provided in example 1 of the present invention;
FIG. 3 is an SEM topography of a solid electrolyte LATP powder provided in example 2 of the present invention;
FIG. 4 is an SEM topography of LATP powder provided by comparative example 1 of the invention;
FIG. 5 is an SEM topography of LATP powder provided by comparative example 2 of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of nanometer solid electrolyte lithium titanium aluminum phosphate comprises the following steps:
step S1: adding a certain amount of water into 10.43g of aluminum chloride, 84.10g of titanium tetrachloride and 90.02g of ammonium dihydrogen phosphate to prepare 1L of mixed salt solution, adding 2mol/L of ammonium bicarbonate solution into the mixed salt solution, adjusting the pH to 8.0 to form white precipitate, continuously stirring for 3h, carrying out suction filtration to obtain precipitate, continuously putting into water for dispersion, and carrying out suction filtration again to obtain the precipitate.
Step S2: preparing 0.1mol/L lithium ion solution by using lithium hydroxide, taking 4.07mL of lithium ion solution, mixing the obtained washed precipitate with the lithium ion solution, adding water to prepare 800mL suspension, transferring into a 1L sealed pressure container, reacting at 80 ℃ for 12h, maintaining the filling pressure in the sealed pressure container at 0.4-0.6 MPa in the reaction process, cooling to room temperature, taking out slurry, and drying at 130 ℃ to obtain LATP precursor powder.
And step S3: calcining the obtained precursor powder at 850 ℃ for 4h to obtain the nano solid electrolyte LATP powder with the particle size D50 being approximately equal to 100nm.
FIG. 1 is an XRD spectrum of the prepared nano-sized solid electrolyte LATP powder, and FIG. 2 is an SEM topography of the prepared nano-sized solid electrolyte LATP powder.
Example 2
A preparation method of nanometer solid electrolyte lithium titanium aluminum phosphate comprises the following steps:
step S1: adding 16.67g of aluminum nitrate, 84.10g of titanium tetrachloride and 90.02g of ammonium dihydrogen phosphate into a certain amount of water to prepare a mixed salt solution of 1L, adding 2mol/L of ammonium bicarbonate solution into the mixed salt solution, adjusting the pH to 8.0 to form a white first precipitate, continuously stirring for 3h, then pumping out the first precipitate, continuously putting the first precipitate into the water, adding 15.03g of lithium carbonate, dispersing, and again pumping out a second precipitate.
Step S2: adding water into the obtained second precipitate to prepare 800mL of suspension, transferring the suspension into a 1L sealed pressure container, reacting for 6h at 100 ℃, and maintaining the filling pressure in the sealed pressure container at 0.4-0.6 MPa in the reaction process; then cooling to room temperature, taking out the slurry, and drying at 100 ℃ to obtain LATP precursor powder;
and step S3: calcining the obtained precursor powder at 900 ℃ for 4h to obtain the nano solid electrolyte LATP powder with the particle size D50 of about 110nm.
FIG. 3 is an SEM topography of the prepared nano-sized solid electrolyte LATP powder.
Example 3
A preparation method of nanometer solid electrolyte lithium titanium aluminum phosphate comprises the following steps:
step S1: adding 6.1g of aluminum hydroxide, 84.10g of titanium tetrachloride and 129.10 g of diammonium hydrogen phosphate into a certain amount of water to prepare 1L of mixed salt solution, adding 2mol/L of ammonium bicarbonate solution into the mixed salt solution, adjusting the pH value to 8.0, continuously stirring for 3 hours after a white precipitate is formed, then carrying out suction filtration on the precipitate, continuously putting the precipitate into water for dispersion, and carrying out suction filtration on the precipitate again.
Step S2: preparing 0.1mol/L lithium ion solution by using lithium hydroxide, taking 4.07mL of the lithium ion solution, mixing the obtained washed precipitate with the lithium ion solution, adding water to prepare 800mL suspension, transferring the suspension into a 1L sealed pressure container, reacting for 12h at 80 ℃, maintaining the filling pressure in the sealed pressure container at 0.4-0.6 MPa in the reaction process, cooling to room temperature, taking out slurry, and drying at 120 ℃ to obtain LATP precursor powder.
And step 3: calcining the obtained precursor powder at 900 ℃ for 4h to obtain the nano solid electrolyte LATP powder with the particle size D50 of about 110nm.
Example 4
A preparation method of nanometer solid electrolyte lithium titanium aluminum phosphate comprises the following steps:
step S1: adding 6.1g of aluminum hydroxide, 150.89g of tetrabutyl titanate and 129.10 g of ammonium hydrogen phosphate into a certain amount of water to prepare 1L of mixed salt solution, adding 2mol/L of ammonium bicarbonate solution into the mixed salt solution, adjusting the pH value to 8.0, continuously stirring for 3 hours after a white precipitate is formed, then carrying out suction filtration on the precipitate, continuously putting the precipitate into water for dispersion, and carrying out suction filtration on the precipitate again.
Step S2: preparing 0.1mol/L lithium ion solution by using lithium hydroxide, taking 4.07mL of the lithium ion solution, mixing the obtained washed precipitate with the lithium ion solution, adding water to prepare 800mL suspension, transferring the suspension into a 1L sealed pressure container, reacting for 6h at 80 ℃, maintaining the filling pressure in the sealed pressure container between 0.4MPa and 0.6MPa in the reaction process, cooling to room temperature, taking out slurry, and drying at 100 ℃ to obtain LATP precursor powder;
and step 3: calcining the obtained precursor powder at 900 ℃ for 4h to obtain the nano solid electrolyte LATP powder with the particle size D50 being approximately equal to 150nm.
Example 5
A preparation method of nanometer solid electrolyte lithium titanium aluminum phosphate comprises the following steps:
step S1: adding a certain amount of water into 10.43g of aluminum chloride, 84.10g of titanium tetrachloride and 90.02g of ammonium dihydrogen phosphate to prepare 1L of mixed salt solution, adding 2mol/L of ammonium bicarbonate solution into the mixed salt solution, adjusting the pH value to 8.0 to form white precipitate, continuously stirring for 3h, carrying out suction filtration to obtain precipitate, continuously putting into water for dispersion, and carrying out suction filtration again to obtain the precipitate.
Step S2: preparing 0.1mol/L lithium ion solution by using lithium hydroxide, taking 4.07mL of the lithium ion solution, mixing the obtained washed precipitate with the lithium ion solution, adding water to prepare 800mL suspension, transferring the suspension into a 1L sealed pressure container, reacting for 6h at 100 ℃, maintaining the filling pressure in the sealed pressure container between 0.4MPa and 0.6MPa in the reaction process, cooling to room temperature, taking out slurry, and drying at 130 ℃ to obtain LATP precursor powder;
and step S3: calcining the obtained precursor powder at 950 ℃ for 4h to obtain the nano solid electrolyte LATP powder, wherein the particle size D50 of the powder is approximately equal to 180nm.
Example 6
A preparation method of nanometer solid electrolyte lithium titanium aluminum phosphate comprises the following steps:
step S1: adding a certain amount of water into 10.43g of aluminum chloride, 84.10g of titanium tetrachloride and 90.02g of ammonium dihydrogen phosphate to prepare 1L of mixed salt solution, adding 2mol/L of ammonium bicarbonate solution into the mixed salt solution, adjusting the pH value to 7.0 to form white precipitate, continuously stirring for 3h, carrying out suction filtration to obtain precipitate, continuously putting into water for dispersion, and carrying out suction filtration again to obtain the precipitate.
Step S2: preparing 0.05mol/L lithium ion solution by using lithium hydroxide, taking 8.14mL of the lithium ion solution, mixing the obtained washed precipitate with the lithium ion solution, adding water to prepare 800mL suspension, transferring the suspension into a 1L sealed pressure container, reacting for 12h at 100 ℃, maintaining the filling pressure in the sealed pressure container at 0.4-0.6 MPa in the reaction process, cooling to room temperature, taking out slurry, and drying at 130 ℃ to obtain LATP precursor powder.
And step S3: calcining the obtained precursor powder at 900 ℃ for 4h to obtain the nano solid electrolyte LATP powder, wherein the particle size D50 of the powder is approximately equal to 130nm.
Example 7
A preparation method of nanometer solid electrolyte lithium titanium aluminum phosphate comprises the following steps:
step S1: adding a certain amount of water into 10.43g of aluminum chloride, 84.10g of titanium tetrachloride and 90.02g of ammonium dihydrogen phosphate to prepare a 1L mixed salt solution, adding 2mol/L ammonium hydrogen carbonate solution into the mixed salt solution, adjusting the pH to 10.0, continuously stirring for 3h after a white precipitate is formed, then carrying out suction filtration on the precipitate, continuously putting into water for dispersion, and carrying out suction filtration on the precipitate again.
Step S2: preparing 0.1mol/L lithium ion solution by using lithium nitrate, taking 4.07mL of the lithium ion solution, adding water into the obtained washed precipitate mixed lithium ion solution to prepare 800mL suspension, transferring the suspension into a 1L sealed pressure container, reacting for 4h at 120 ℃, maintaining the filling pressure in the sealed pressure container between 0.4MPa and 0.6MPa in the reaction process, cooling to room temperature, taking out slurry, and drying at 130 ℃ to obtain LATP precursor powder.
And step S3: calcining the obtained precursor powder at 800 ℃ for 10h to obtain the nano solid electrolyte LATP powder, wherein the particle size D50 of the powder is approximately equal to 110nm.
Comparative example 1
The preparation method of the solid electrolyte lithium titanium aluminum phosphate comprises the following steps:
step S1: adding 6.1g of aluminum hydroxide, 84.10g of titanium tetrachloride and 129.10 g of diammonium hydrogen phosphate into a certain amount of water to prepare 1L of mixed salt solution, adding 2mol/L of ammonium bicarbonate solution into the mixed salt solution, adjusting the pH value to 8.0, continuously stirring for 3 hours after a white precipitate is formed, then carrying out suction filtration on the precipitate, continuously putting the precipitate into water for dispersion, and carrying out suction filtration on the precipitate again.
Step S2: preparing 0.1mol/L lithium ion solution by using lithium hydroxide, taking 4.07mL of the lithium ion solution, mixing the obtained washed precipitate with the lithium ion solution, adding water to prepare 800mL of suspension, and drying the suspension at 120 ℃ to obtain LATP precursor powder.
And step S3: calcining the obtained precursor powder at 900 ℃ for 4h to obtain the LATP powder, wherein the particle size D50 of the obtained powder is approximately equal to 1 mu m.
FIG. 4 is an SEM image of the prepared LATP powder.
Comparative example 2
The preparation method of the solid electrolyte lithium titanium aluminum phosphate comprises the following steps:
step S1: 6.1g of aluminum hydroxide, 150.89g of tetrabutyl titanate and 129.10 g of ammonium hydrogen phosphate were added to a certain amount of water to prepare a 1L mixed salt solution, and a 2mol/L ammonium hydrogen carbonate solution was added to the mixed salt solution to adjust the pH to 8.0, thereby forming a white precipitate. Mixing the precipitate with 4.07mL of 0.1mol/L lithium ion solution, adding water to prepare 800mL of suspension, transferring the suspension into a 1L sealed pressure container, reacting at 100 ℃ for 6h, maintaining the filling pressure in the sealed pressure container at 0.4-0.6 MPa in the reaction process, cooling to room temperature, taking out slurry, and drying at 100 ℃ to obtain LATP precursor powder;
step S2: calcining the obtained precursor powder at 900 ℃ for 4h to obtain the LATP powder. The obtained LATP powder has serious particle size agglomeration, and the secondary particle size is more than 20 mu m.
FIG. 5 is an SEM image of the prepared LATP powder.
From the experimental results of the above examples, it can be seen that a nano solid electrolyte LATP having a particle size of less than 200nm can be obtained by the preparation method of the present invention. As can be seen from the results of the comparative experiments of example 3 and comparative example 1, the hydrothermal treatment process in step S2 has an important influence on the particle size of the final solid electrolyte LATP of the present invention, and the particle size of the solid electrolyte LATP obtained without the hydrothermal treatment process is on the micron level and large. As can be seen from the results of the comparative experiments of example 3 and comparative example 2, the washing of the precipitate in step S1 also has an important influence on the particle size of the final LATP of the solid electrolyte of the present invention, and the solid electrolyte LATP obtained without washing the precipitate has serious agglomeration of particles, the particle size is in the micrometer range, and the particle size is large.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of nanometer solid electrolyte lithium titanium aluminum phosphate is characterized by comprising the following steps:
step S1: preparing raw materials according to the stoichiometric ratio of the lithium aluminum titanium phosphate, preparing a precipitate by using the raw materials, and washing the precipitate; wherein, the atomic ratio of the raw materials satisfies: li: al: ti: p = (1 + x): x: (2-x): x is more than or equal to 3,0 and less than or equal to 0.5; water is used as a solvent in the process of preparing the precipitate;
step S2: adding water into the washed precipitate to prepare a suspension, moving the suspension into a sealed pressure container, reacting for a period of time at a certain temperature, and drying the reacted material to obtain precursor powder;
and step S3: and carrying out heat treatment on the precursor powder to obtain the solid electrolyte lithium titanium aluminum phosphate.
2. The method of claim 1, comprising the steps of:
step S1: adding an aluminum source, a titanium source and a phosphorus source into water to prepare a mixed salt solution; dropwise adding an alkaline solution into the mixed salt solution until the pH value is 7-10 to form the precipitate; washing the precipitate with water for 1-3 times;
step S2: uniformly mixing the washed precipitate with a lithium ion solution, adding water to prepare a suspension, transferring the suspension into a sealed pressure container, and reacting at 80-130 ℃ for 2-12 h; then drying the reacted materials to obtain precursor powder;
and step S3: and carrying out heat treatment on the precursor powder to obtain the solid electrolyte lithium titanium aluminum phosphate.
3. The method of claim 1, comprising the steps of:
step S1: adding an aluminum source, a titanium source and a phosphorus source into water to prepare a mixed salt solution, and dropwise adding an alkaline solution into the mixed salt solution until the pH value is 7-10 to form a first precipitate; putting the first precipitate into water, adding lithium salt into the water, fully dispersing, and performing suction filtration to obtain a second precipitate;
step S2: adding water into the second precipitate to prepare the suspension, then transferring the suspension into a sealed pressure container, and reacting for 2-12 h at 80-130 ℃; then drying the reacted materials to obtain precursor powder;
and step S3: and carrying out heat treatment on the precursor powder to obtain the solid electrolyte lithium titanium aluminum phosphate.
4. The preparation method according to claim 2 or 3, wherein the aluminum source comprises one or more of aluminum nitrate, aluminum chloride and aluminum hydroxide;
and/or the titanium source comprises one or more of tetrabutyl titanate and titanium tetrachloride;
and/or the phosphorus source comprises one or more of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
5. The method of claim 2, wherein the lithium ion solution comprises one or more of a lithium hydroxide solution, a lithium nitrate solution, and a lithium acetate solution.
6. The method of claim 3, wherein the lithium salt comprises lithium carbonate.
7. The method of claim 1, wherein a filling pressure within the sealed pressure vessel is maintained between 0.4MPa and 0.6MPa.
8. The method according to claim 1, wherein the heat treatment is performed at 800-950 ℃ for 1-10 h in step S3.
9. A nano-sized solid electrolyte lithium titanium aluminum phosphate, which is prepared by the preparation method of any one of claims 1 to 8; the solid electrolyte lithium titanium aluminium phosphate has a D50<200nm.
10. Use of the solid electrolyte lithium titanium aluminium phosphate prepared by the preparation method according to any one of claims 1 to 8 or the solid electrolyte lithium titanium aluminium phosphate according to claim 9 in a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211262306.5A CN115458804A (en) | 2022-10-14 | 2022-10-14 | Nano solid electrolyte lithium titanium aluminum phosphate, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211262306.5A CN115458804A (en) | 2022-10-14 | 2022-10-14 | Nano solid electrolyte lithium titanium aluminum phosphate, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115458804A true CN115458804A (en) | 2022-12-09 |
Family
ID=84309998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211262306.5A Pending CN115458804A (en) | 2022-10-14 | 2022-10-14 | Nano solid electrolyte lithium titanium aluminum phosphate, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115458804A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118637585A (en) * | 2024-08-12 | 2024-09-13 | 材料科学姑苏实验室 | Solid electrolyte lithium titanium aluminum phosphate precursor and preparation method and application thereof |
-
2022
- 2022-10-14 CN CN202211262306.5A patent/CN115458804A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118637585A (en) * | 2024-08-12 | 2024-09-13 | 材料科学姑苏实验室 | Solid electrolyte lithium titanium aluminum phosphate precursor and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20010012275A (en) | Novel process for preparing spinel type lithium manganese composite oxide and cathode active material for rechargeable battery | |
| KR101191155B1 (en) | Synthesizing method for lithium titanium oxide nanoparticle using supercritical fluids | |
| JP2015525182A (en) | Method for producing graphene-based LiFePO4 / C composite material | |
| KR20120079058A (en) | Ferric phosphate hydrate particle powder and process for production thereof, olivine-type lithium iron phosphate particle powder and process for production thereof, and non-aqueous electrolyte secondary battery | |
| CN102745662B (en) | Preparation method of amorphous iron phosphate | |
| JP2015502911A (en) | Manganese-containing metal phosphate and method for producing the same | |
| CN112125292A (en) | Hydrothermal synthesis method of lithium manganese iron phosphate | |
| CN112266020B (en) | Method for preparing vanadium pentoxide cathode material from sodium vanadium solution | |
| JP6528890B1 (en) | Method of manufacturing electrode material, method of recovering lithium phosphate | |
| CN114572957B (en) | Preparation method of sodium vanadium phosphate material | |
| CN115458804A (en) | Nano solid electrolyte lithium titanium aluminum phosphate, preparation method and application | |
| CN109678166B (en) | Preparation of sodium titanium silicate material and application of sodium titanium silicate material in lithium/sodium ion battery | |
| CN113285071B (en) | Lithium iron phosphate and preparation method and application thereof | |
| CN113348150B (en) | Titanium oxide, method for producing titanium oxide, and lithium secondary battery using electrode active material containing titanium oxide | |
| JP2019220379A (en) | Method for manufacturing latp crystal grains for solid electrolyte of secondary battery | |
| KR101684387B1 (en) | Method for Preparation of Olivine Type Lithium Manganese Iron Phosphate and Product Obtained from the Same | |
| CN110713197B (en) | Method for recovering lithium salt from mother solution generated in preparation of lithium iron phosphate by hydrothermal method | |
| CN101209961B (en) | Method for preparing ferrous oxalate hydrated salt crystal | |
| CN112938916B (en) | Synthesis method for preparing lithium iron phosphate precursor with high cost performance by controlling crystallization | |
| CN112615045B (en) | Electrolyte material for solid lithium ion battery and preparation method thereof | |
| KR101684385B1 (en) | Method for Preparation of Olivine Type Lithium Iron Phosphate | |
| CN115974036A (en) | Spherical lithium ferric manganese phosphate nano-particles and preparation method thereof | |
| KR20140064356A (en) | Method for preparation of olivine type lithium manganese iron phosphate and product obtained from the same | |
| KR101565300B1 (en) | Method for Preparation of Olivine Type Lithium Manganese Phosphate and Product Obtained from the Same | |
| KR20220154218A (en) | Alternative Methods for Manufacturing Lithium Battery Cathode Materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |