CN115377485A - Phosphate material and lithium ion battery - Google Patents

Phosphate material and lithium ion battery Download PDF

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CN115377485A
CN115377485A CN202211315308.6A CN202211315308A CN115377485A CN 115377485 A CN115377485 A CN 115377485A CN 202211315308 A CN202211315308 A CN 202211315308A CN 115377485 A CN115377485 A CN 115377485A
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phosphate
lithium
source
titanium
aluminum
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李立飞
邹魁
朱程琦
李延凤
赵辉
何培琪
黄韬
潘珂
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Jiangsu Langu New Energy Technology Co ltd
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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Abstract

The invention relates to the technical field of lithium ion batteries, and provides a phosphate material and a lithium ion battery. The phosphate material comprises titanium aluminum lithium phosphate, aluminum phosphate and titanium lithium oxygen phosphate, wherein the content of the titanium aluminum lithium phosphate is 50-95wt%, the content of the aluminum phosphate is 2-20wt%, and the content of the titanium lithium oxygen phosphate is 2-30wt%. The phosphate material provided by the application is composed of LATP and AlPO 4 And Litiopo 4 The anode material, the cathode material and the lithium ion battery are uniformly distributed, have certain ionic conductivity, can remove residual lithium on the surface of the ternary material when being applied to anode coating, and can improve the electrochemical performance of the anode material by uniformly coating the LATP solid electrolyte material on the surface of the anode material.

Description

Phosphate material and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a phosphate material and a lithium ion battery.
Background
Lithium ion batteries have received much attention from people because of their advantages of high energy density, long service life, low self-discharge, no memory effect, and environmental protection. Since their first successful commercialization in 1991, sony corporation has seen lithium ion battery technology, lithium ion batteries have gained a great deal of use in consumer electronics devices such as cell phones, laptop computers, cameras, and the like. At present, commercial lithium ion batteries mainly use organic electrolyte, and have potential safety hazards such as liquid leakage, combustion, explosion and the like in unconventional environments. The research and development and industrialization based on the inorganic solid electrolyte material have important significance for solving the safety problem of the traditional liquid battery.
At present, solid electrolyte materials are mainly divided into four systems of oxides, sulfides, polymers and halides. Among them, the oxide solid electrolyte material has the advantages of easily available raw materials, relatively simple preparation process, strong compatibility with the existing cell process, and the like, and thus becomes the solid electrolyte material with the greatest commercial prospect. The oxide solid electrolyte material is mainly applied to three application fields of anode coating, diaphragm coating and coating of anode/cathode pole pieces at present by combining the existing battery cell process procedures.
The positive electrode material is the most critical part of the lithium ion battery, and the cost of the positive electrode material accounts for about one third of the whole battery. The ternary material is the preferred anode material of the high-energy density lithium ion battery at present. However, the ternary material is easy to absorb moisture and CO when exposed to air 2 React with residual lithium on the surface layer to form LiOH and Li 2 CO 3 Further increases the pH value of the material, and also seriously influences the electrochemical performance and the storage performance of the ternary material. The excessive pH value of the ternary material can cause slurry gelation in the process of preparing the electrode plate, so that the coating is not uniform. In another aspect, the material particlesResidual lithium on the surface has poor conductivity, which increases the polarization of the battery.
At present, most material manufacturers adopt a process of water washing and secondary sintering to reduce surface residual alkali, but the method can damage the surface structure of the material and reduce the capacity. Aiming at the problems, researchers carry out a great amount of scientific researches and experiments, and the results show that the surface residual alkali of the ternary material can be effectively reduced through surface coating. However, although coating with alumina, silica, or the like can reduce surface alkali residues, oxides such as alumina, silica, or the like do not have ion conductivity and inhibit ion diffusion; therefore, the material with the ionic conductivity can effectively solve the surface alkali residue and simultaneously has the ionic conductivity.
The coating of the solid electrolyte material is carried out on the positive and negative pole pieces, and the nano-scale solid electrolyte material can be filled in the gaps and the surfaces of the positive and negative pole pieces, so that the contact area of the electrolyte and the positive and negative pole pieces is reduced, the side reaction of the electrolyte is inhibited, the thermal stability, the electrochemical stability and the like of the positive and negative pole pieces are improved, and the safety performance of the battery is improved. Currently, the prior art generally adopts a LATP material with an NASICON structure for coating of a positive electrode material and coating of a positive/negative electrode plate; or directly using AlPO 4 And coating the positive electrode material.
Although the conventional LATP material with the NASICON structure has a certain ionic conductivity, because the LATP material can form a phase only by high-temperature sintering, in order to prevent a lithium-deficient phase caused by lithium volatilization, an excessive lithium source is usually added in the LATP sintering process, and the excessive rate of the lithium source is usually 5 to 10%. Therefore, residual lithium is generally present on the surface of the fired LATP, and the pH value is 7.5 to 8. When the anode is coated, the crystal structure of the anode material is affected by the current scheme of water washing due to the surface alkalinity of the ternary material of the anode. If the fired LATP is directly used for coating, the alkalinity reducing effect on the anode ternary material is very small; in the process of homogenizing the anode material, the PVDF is subjected to defluorination and gelation. While using AlPO 4 Coating the anode ternary material due to AlPO 4 Does not contain Li element, and AlPO is coated on the positive electrode 4 With Li remaining on the surface of the positive electrode material 2 CO 3 React to form Li 3 PO 4 Meanwhile, al element diffuses into the anode material.
Disclosure of Invention
The invention aims to provide a phosphate material, and the phosphate material provided by the application can improve the electrochemical performance of a positive electrode material.
In view of the above, the present application provides a phosphate material, which is composed of titanium aluminum lithium phosphate, aluminum phosphate and titanium lithium oxide phosphate, wherein the content of the titanium aluminum lithium phosphate is 50 to 95wt%, the content of the aluminum phosphate is 2 to 20wt%, and the content of the titanium lithium oxide phosphate is 2 to 30wt%.
Preferably, the content of the titanium aluminum lithium phosphate is 65-90wt%, the content of the aluminum phosphate is 2.5-15wt%, and the content of the titanium lithium phosphate is 2.5-20wt%.
The application also provides a preparation method of the phosphate material, which comprises the following steps:
a) According to the proportion of a phosphate material, carrying out dry mixing or wet mixing on a lithium source, a titanium source, a phosphorus source and an aluminum source to obtain mixed powder;
b) And sintering the mixed powder to obtain the phosphate material.
Preferably, the dry mixing specifically comprises:
and (3) mixing the lithium source, the titanium source, the phosphorus source and the aluminum source in a high-speed mixer, a vertical mixer or a double helix conical mixer for 10 to 90min.
Preferably, the wet mixing specifically comprises:
mixing a lithium source, a titanium source, a phosphorus source and an aluminum source in a solvent to obtain slurry;
and (3) carrying out planetary ball milling, stirring milling or sand milling on the slurry for 3-6 h, drying at 100-150 ℃, and then grinding and sieving.
Preferably, the content of the powder in the slurry is 15 to 45wt%.
Preferably, the temperature rise speed of the sintering is 2 to 5 ℃/min, the temperature of the sintering is 500 to 1500 ℃, and the time is 6 to 12h.
Preferably, the lithium source is selected from one or more of lithium carbonate, lithium hydroxide, lithium phosphate, lithium dihydrogen phosphate, lithium acetate and lithium nitrate, the titanium source is selected from one or more of titanium dioxide, titanium pyrophosphate and titanium phosphate, and the phosphorus source is selected from ammonium dihydrogen phosphate; the aluminum source is one or two selected from aluminum hydroxide and aluminum oxide.
The application also provides a lithium ion battery which comprises a positive electrode, a negative electrode and a solid electrolyte, and is characterized in that the solid electrolyte is selected from the phosphate material or the phosphate material prepared by the preparation method.
Preferably, the material of the positive electrode is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.8 and less than 0.9, and y is more than 0 and less than or equal to 0.1.
In contrast to the prior art, the present application provides a phosphate material consisting of Lithium Aluminum Titanium Phosphate (LATP), aluminum phosphate (AlPO) 4 ) And lithium titanyl phosphate (LiTiOPO) 4 ) The anode material, the cathode material and the LATP solid electrolyte material are uniformly distributed, have certain ionic conductivity, can remove residual lithium on the surface of the ternary material when applied to anode coating, and simultaneously uniformly coat the LATP solid electrolyte material on the surface of the anode material, thereby improving the electrochemical performance of the anode material.
Further, the application also provides a preparation method of the phosphate material, which comprises the steps of selecting a phosphorus source, a titanium source, an aluminum source and a lithium source in a ratio, performing solid phase sintering, and performing solid phase reaction by diffusion of Li, ti, P and Al elements to form a solid solution, so that LATP and AlPO are obtained 4 And Litiopo 4 The three phosphate materials are mixed homogeneously, so that the electrochemical performance of the anode material is further improved.
Drawings
Fig. 1 is an XRD pattern of the phosphate material prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the present invention, reference will now be made to the following preferred embodiments of the invention in conjunction with the examples, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and is not intended to limit the scope of the claims which follow.
In view of the performance defects of the solid electrolyte material in the prior art, the application provides a phosphate material and a preparation method thereof, and the phosphate material provided by the application can ensure the stability of the anode material besides the function of ensuring ion conduction, thereby ensuring the electrochemical performance of the anode material. Specifically, the embodiment of the invention discloses a phosphate material which comprises titanium aluminum lithium phosphate, aluminum phosphate and titanium lithium oxide phosphate, wherein the content of the titanium aluminum lithium phosphate is 50-95wt%, the content of the aluminum phosphate is 2-20wt%, and the content of the titanium lithium oxide phosphate is 2-30wt%.
Specifically, in the application, the content of the titanium aluminum lithium phosphate is 65 to 90wt%, the content of the aluminum phosphate is 2.5 to 15wt%, and the content of the titanium lithium phosphate oxide is 2.5 to 20wt%; more specifically, the content of lithium aluminum titanium phosphate is 65wt%, 68wt%, 72wt%, 75wt%, 80wt%, 83wt%, 86wt%, or 90wt%; the aluminum phosphate is present in an amount of 2.5, 5, 7, 9, 10, 12, or 15wt%; the content of the lithium aluminum titanium phosphate is 2.5wt%, 5.5wt%, 7.5wt%, 10wt%, 15wt%, 17wt%, 18wt% or 20wt%.
The application also provides a method for preparing a phosphate material, comprising the following steps:
a) According to the proportion of phosphate material components, carrying out dry mixing or wet mixing on a lithium source, a titanium source, a phosphorus source and an aluminum source to obtain mixed powder;
b) And sintering the mixed powder to obtain the phosphate material.
In the process of preparing the phosphate material, the method does not adopt a mode of directly mixing all components, but prepares the raw materials according to the mixture ratio of the components, and carries out solid-phase sintering on the raw materials to obtain the phosphate material with three phases uniformly mixed.
Specifically, the raw materials are firstly mixed according to the proportion of each component in the finished phosphate material, namely, a lithium source, a titanium source, phosphoric acid and an aluminum source are mixed by a dry method or a wet method to obtain mixed powder; the dry mixing is to perform dry mixing of powder by using mixing equipment such as a high-speed mixer, a vertical mixer or a double-helix conical mixer, wherein the linear speed of the mixing equipment is 5 to 40m/s, and the mixing time is 10 to 90min. The wet mixing is to mix a lithium source, a titanium source, a phosphorus source and an aluminum source in a solvent to obtain slurry; and then carrying out planetary ball milling, stirring milling or sand milling on the slurry for 3-6 h, drying at 100-150 ℃, and then grinding and sieving. In the wet mixing process, the solvent may be selected from water, ethanol or isopropanol. The ball-to-feed ratio of grinding is 5 to 20 (the ball-to-feed ratio is grinding ball mass: powder mass), and specifically the ball-to-feed ratio is 6 to 10; the grinding balls are well known to those skilled in the art and may be exemplified by zirconia balls, alumina balls or agate balls, and in this application, the grinding balls are zirconia balls. The diameter of the grinding ball is 0.3-5mm, and more specifically, the diameter of the grinding ball is 1-3mm. The content of the powder in the slurry is 15-45wt%, and more specifically, the content of the components in the slurry is 20-40wt%.
In the present application, the lithium source is selected from one or more of lithium carbonate, lithium hydroxide, lithium phosphate, lithium dihydrogen phosphate, lithium acetate and lithium nitrate, the titanium source is selected from one or more of titanium dioxide, titanium pyrophosphate and titanium phosphate, and the phosphorus source is selected from ammonium dihydrogen phosphate; the aluminum source is one or two selected from aluminum hydroxide and aluminum oxide.
According to the invention, after the mixed powder is obtained, the mixed powder is subjected to solid-phase sintering to obtain a phosphate material; in the process, titanium element, phosphorus element, lithium element and aluminum element are subjected to solid-phase reaction, element diffusion is carried out to form a solid solution, and further LATP and AlPO are ensured 4 And Litiopo 4 Are mixed homogeneously. In the sintering process, the temperature rising speed is 2 to 5 ℃/min, the sintering temperature is 500 to 1200 ℃, and the time is 6 to 12h; more specifically, the sintering temperature is 800-1000 ℃, and the sintering time is 8-10 h.
And after the sintering, finally taking out the sintered phosphate material, and grinding the phosphate material through a 200-mesh screen to obtain the phosphate material.
The application also provides a lithium ion battery which comprises a positive electrode, a negative electrode and a solid electrolyte, wherein the solid electrolyte is the phosphate material prepared by the scheme.
More specifically, the phosphate materials provided herein can be used as solid electrolyte materials for the packaging of positive electrode materialsCovering; the method specifically comprises the following steps: the phosphate material is subjected to nanocrystallization through crushing means such as airflow powder, sanding and the like; phosphate material passes through a coating machine to be mixed with anode ternary material LiNi x Co y Mn 1-x-y O 2 X is more than or equal to 0.8 and less than 0.9, y is more than 0 and less than or equal to 0.1, the temperature of the coated material is raised to 800 to 950 ℃ at the speed of 2 to 5 ℃/min, the temperature is kept for 6 to 12h, and the anode material coated by the phosphate solid electrolyte material can be obtained after natural cooling. The present application provides a lithium ion battery, in which the cathode material is well known to those skilled in the art, and the present application is not particularly limited, and for example, the cathode material may be selected from LiNi 0.8 Co 0.1 Mn 0.1 O 2 Or LiNi 0.83 Co 0.1 Mn 0.07 O 2 。
The present application provides a phosphate material that incorporates AlPO and a method of making the same 4 、LiTiOPO 4 Compared with the advantages of the LATP material, the phosphate material is directly fired in one step through the model selection and formula adjustment of the initial raw materials, and the AlPO in the material is simple to mix 4 、LiTiOPO 4 The combination with the three phases of LATP is more uniform; the phosphate material can reduce the alkalinity of the ternary material, avoid the crystal structure change of the ternary material caused by a water system ternary material, improve the thermal stability of the anode material and improve the safety performance of the battery; compared with the addition of the traditional LATP material, the added positive/negative pole piece or the added coated material not only can achieve the effect of ion conduction, but also can improve the capacity; in AlPO 4 /LiTiOPO 4 In LATP three phases, alPO 4 The lithium-free phase can preferentially react with residual lithium on the surface of the ternary material of the positive electrode to generate Li when the positive electrode is coated 3 PO 4 Under the drive of concentration gradient, al element diffuses to LiTiOPO 4 In the lattice, the LATP material with the NASICON structure is generated in situ, so that Al element is prevented from diffusing into the anode material and influencing the electrical property of the anode material; compared with AlPO 4 、LiTiOPO 4 Directly mixing the three materials with LATP according to the proportion, the phosphate material is sintered by solid phase, and Li, ti, O, P and Al elements are sintered by solid phaseThe element is diffused to form solid solution by reaction, which is more beneficial to the diffusion of Al element to LiTiOPO 4 In situ, a LATP material of NASICON structure is generated.
For further understanding of the present invention, the phosphate material and the lithium ion battery provided by the present invention are described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
1. Preparing materials:
1. according to LATP, alPO 4 、LiTiOPO 4 In this example, the ratio of LATP is 65%, alPO 4 15% of LiTiOPO 4 20 percent of the total weight; calculating lithium source, titanium source, phosphorus source and aluminum source according to the proportion, and selecting Li 2 CO 3 As a lithium source, ti 3 （PO 4 ） 4 (titanium phosphate) as phosphorus and titanium sources, NH 4 H 2 PO 4 (monoammonium phosphate) as a supplemental phosphorus source, al 2 O 3 (alumina) as an aluminium source;
33.62g Li were weighed 2 CO 3 ，322.81g Ti 3 （PO 4 ） 4 ，74g NH 4 H 2 PO 4 ，20.90g Al 2 O 3 (ii) a Pouring the weighed powder into 1805g of water, wherein the mass of the powder accounts for 20% of the total mass of the slurry;
2. grinding the slurry for 6h by planetary ball milling, wherein the ball-to-material ratio is 5 (ball-to-material ratio is the mass of grinding balls: the mass of powder), weighing 2256g of 3mm zirconia balls;
3. after grinding, drying the slurry at 120 ℃, drying to obtain powder aggregated into blocks, and grinding the powder through a 200-mesh screen by using a mortar;
4. grinding the sieved powder, placing the powder in an alumina crucible, heating to 1000 ℃ at the speed of 2 ℃/min, preserving heat for 12h, and naturally cooling;
5. and taking out the cooled phosphate material, and grinding the phosphate material through a 200-mesh screen to obtain the phosphate solid electrolyte material. Fig. 1 is an XRD spectrum of the phosphate solid electrolyte material prepared in this example, from fig. 1, in which 27.046 °, 27.422 °, 27.969 ° represent phase peaks of lithium titanyl phosphate, 21.783 ° represents phase peaks of aluminum phosphate, and the remaining diffraction peaks represent phase peaks of lithium titanium aluminum phosphate (LATP).
2. Use 1-coating of positive electrode
1. Grinding the phosphate solid electrolyte material to be nano-sized;
2. the nano phosphate solid electrolyte material passes through a coating machine to be mixed with a positive ternary material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Coating, heating the coated material to 800 ℃ at a speed of 5 ℃/min, preserving heat for 6 hours, and naturally cooling to obtain the phosphate solid electrolyte material coated anode material;
3. electrochemical testing
Assembling 2032 button cell in a glove box filled with argon, controlling the water oxygen value in the glove box to be less than 0.01ppm, using the coated ternary material as a positive electrode, polypropylene as a diaphragm, foamed nickel as a structural support and electric conduction, using a metal lithium sheet as a negative electrode, and using 1M LiPF 6 A mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (EMC) (volume ratio 1.
The battery is tested under the constant temperature condition of 25 ℃, and the charging and discharging modes are as follows: constant current charging and constant voltage charging for 30 minutes, and constant current discharging; for the test of the cycle performance, the battery is firstly activated by charging and discharging with 0.1C low current for three times, and then charged and discharged with 0.5C constant current for 100 times. For the rate performance test, the battery is charged and discharged at constant current of 0.5C and 5C within the voltage range of 2.75-4.3V. The test results are shown in table 1.
Example 2
1. Preparing materials:
1. according to LATP, alPO 4 、LiTiOPO 4 In this embodiment, the ratio of LATP to AlPO is 90% 4 5% of LiTiOPO 4 5 percent of the total weight of the alloy, calculating a lithium source, a titanium source, a phosphorus source and an aluminum source according to the proportion, and selectingLi 2 CO 3 As a source of lithium, NH 4 H 2 PO 4 As a source of phosphorus and TiO 2 As a titanium source, al 2 O 3 As an aluminum source;
51.723g of Li were weighed 2 CO 3 ，345.075g NH 4 H 2 PO 4 ，20.392g Al 2 O 3 ，127.784 TiO 2 Pouring weighed powder into 2179.89g of water, wherein the mass of the powder accounts for 20% of the total mass of the slurry;
2. grinding the slurry for 6 hours by a planetary ball milling process, wherein the ball-to-material ratio is 5 (the ball-to-material ratio is the mass of a grinding ball: the mass of powder), and weighing 2724.87g of 5mm zirconia balls;
3. after grinding, drying the slurry at 120 ℃, drying to obtain powder agglomerated into a block, and grinding the powder through a 200-mesh screen by using a mortar;
4. grinding the sieved powder, placing the powder in an alumina crucible, heating to 1000 ℃ at the speed of 2.5 ℃/min, preserving heat for 12 hours, and naturally cooling;
5. and taking out the cooled phosphate material, and grinding the phosphate material through a 200-mesh screen to obtain the phosphate solid electrolyte material.
2. Use 1-coating of positive electrode
1. The phosphate solid electrolyte material is subjected to nanocrystallization through sanding;
2. the phosphate solid electrolyte material after the nanocrystallization passes through a coating machine to be mixed with a positive ternary material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Coating, heating the coated material to 850 ℃ at a speed of 5 ℃/min, preserving heat for 8h, and naturally cooling to obtain the phosphate solid electrolyte material coated anode material;
3. electrochemical testing was the same as in example 1. The test results are shown in table 1.
Example 3
1. Preparing materials:
1. according to LATP, alPO 4 、LiTiOPO 4 In this embodiment, the ratio of LATP to AlPO is 95% 4 2.5% by weight, liTiOPO 4 2.5% by weight, based on the above ratioCalculating a lithium source, a titanium source, a phosphorus source and an aluminum source; selection of LiOH. H 2 O as a lithium source ， TiP 2 O 7 (titanium Pyrophosphate) as phosphorus and titanium Source, NH 4 H 2 PO 4 (monoammonium phosphate) as a supplemental phosphorus source, al (OH) 3 (aluminum hydroxide) as an aluminum source;
weigh 58.748g LiOH. H 2 O，115.025g NH 4 H 2 PO 4 ，31.201g Al（OH） 3 ，354.893g TiP 2 O 7 Pouring the weighed powder into 1306.357g of water, wherein the mass of the powder accounts for 30% of the total mass of the slurry;
2. grinding the slurry for 8 hours by a stirring and grinding process, wherein the ball-to-feed ratio is 6 (the ball-to-feed ratio is the mass of grinding balls: the mass of powder), and weighing 3359.203g of 5mm zirconia balls;
3. after grinding, drying the slurry at 120 ℃, drying to obtain powder agglomerated into a block, and grinding the powder through a 200-mesh screen by using a mortar;
4. grinding the sieved powder, placing the powder in an alumina crucible, heating to 1000 ℃ at the speed of 2.5 ℃/min, preserving heat for 8 hours, and naturally cooling;
5. and taking out the cooled phosphate material, and grinding the phosphate material through a 200-mesh screen to obtain the phosphate solid electrolyte material.
2. Use 1-positive electrode coating
1. Grinding the phosphate solid electrolyte material to be nano-sized;
2. the phosphate solid electrolyte material after the nanocrystallization passes through a coating machine to be mixed with a positive ternary material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Coating, heating the coated material to 900 ℃ at a speed of 5 ℃/min, preserving heat for 6h, and naturally cooling to obtain the phosphate solid electrolyte material coated anode material;
3. electrochemical testing was the same as in example 1. The test results are shown in table 1.
Example 4
1. Preparing materials:
1. according to LATP, alPO 4 、LiTiOPO 4 In this example, the ratio of LATP to AlPO is 80% 4 15% of LiTiOPO 4 5 percent of the total weight of the alloy, and calculating a lithium source, a titanium source, a phosphorus source and an aluminum source according to the proportion; selection of LiOH. H 2 O as a lithium source ， TiP 2 O 7 (titanium Pyrophosphate) as phosphorus and titanium Source, NH 4 H 2 PO 4 (monoammonium phosphate) as a supplemental phosphorus source, al (OH) 3 (aluminum hydroxide) as an aluminum source;
weigh 58.748g LiOH. H 2 O，186.491g NH 4 H 2 PO 4 ，37.563g Al（OH） 3 ，354.893g TiP 2 O 7 Pouring weighed powder into 1184.291g of water, wherein the weight of the powder accounts for 35% of the total weight of the slurry;
2. grinding the slurry for 12h by a sand grinding process, wherein the ball-to-feed ratio is 5 (ball-to-feed ratio is the mass of grinding balls: the mass of powder), and weighing 3188.475g of zirconia balls with the diameter of 3 mm;
3. after grinding, drying the slurry at 120 ℃, drying to obtain powder agglomerated into a block, and grinding the powder through a 200-mesh screen by using a mortar;
4. grinding the sieved powder, placing the powder in an alumina crucible, heating to 950 ℃ at the speed of 2.5 ℃/min, preserving heat for 8 hours, and naturally cooling;
5. and taking out the cooled phosphate material, and grinding the phosphate material through a 200-mesh screen to obtain the phosphate solid electrolyte material.
2. Use 1-positive electrode coating
1. The phosphate solid electrolyte material is subjected to nanocrystallization through sanding;
2. the phosphate solid electrolyte material after the nanocrystallization passes through a coating machine to be mixed with a positive ternary material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Coating, heating the coated material to 900 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and naturally cooling to obtain the phosphate solid electrolyte material coated anode material;
3. electrochemical testing was the same as in example 1. The test results are shown in table 1.
Example 5
1. Preparing materials:
1. according to LATP, alPO 4 、LiTiOPO 4 In this example, the ratio of LATP to AlPO is 80% 4 15% of LiTiOPO 4 5 percent of the total weight of the alloy, and calculating a lithium source, a titanium source, a phosphorus source and an aluminum source according to the proportion; selection of LiOH. H 2 O as a lithium source, tiP 2 O 7 (titanium Pyrophosphate) as phosphorus and titanium sources, NH 4 H 2 PO 4 (monoammonium phosphate) as a source of supplemental phosphorus, al (OH) 3 (aluminum hydroxide) as an aluminum source, 58.748g of LiOH. H was weighed 2 O，186.491g NH 4 H 2 PO 4 ，37.563g Al（OH） 3 ，354.893g TiP 2 O 7 ；
2. Feeding the raw materials into a mixing device of a double-helix conical mixer to perform dry mixing of powder, wherein the linear speed is 10m/s, and the mixing time is 60min;
3. placing the mixed powder in an alumina crucible, heating to 950 ℃ at the speed of 2.5 ℃/min, preserving heat for 8 hours, and naturally cooling;
4. and taking out the cooled phosphate material, and grinding the phosphate material through a 200-mesh screen to obtain the phosphate solid electrolyte material.
2. Use 1-coating of positive electrode
1. The phosphate solid electrolyte material is subjected to nanocrystallization through sanding;
2. the phosphate solid electrolyte material after the nanocrystallization passes through a coating machine to be mixed with a positive ternary material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Coating, heating the coated material to 900 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and naturally cooling to obtain the phosphate solid electrolyte material coated anode material;
3. electrochemical test As in example 1
This example five is different from example four in that this example uses a dry mixing device. The test results are shown in table 1.
Example 6
1. Preparing materials:
1. according to LATP, alPO 4 、LiTiOPO 4 In this example, the ratio of LATP to AlPO is 90% 4 5% by weight of LiTiOPO 4 5 percent of the total weight of the alloy, and calculating a lithium source, a titanium source, a phosphorus source and an aluminum source according to the proportion; selection of Li 2 CO 3 As a source of lithium, NH 4 H 2 PO 4 As a source of phosphorus and TiO 2 As a titanium source, al 2 O 3 51.723g of Li was weighed as an aluminum source 2 CO 3 ，345.075g NH 4 H 2 PO 4 ，20.392g Al 2 O 3 ，127.784 TiO 2 ；
2. Feeding the raw materials into a mixing device of a high-speed mixer for dry mixing of powder, wherein the linear speed is 30m/s, and the mixing time is 50min;
3. placing the mixed powder in an alumina crucible, heating to 950 ℃ at the speed of 2.5 ℃/min, preserving heat for 8 hours, and naturally cooling;
4. and taking out the cooled phosphate material, and grinding the phosphate material through a 200-mesh screen to obtain the phosphate solid electrolyte material.
2. Use 1-positive electrode coating
1. The phosphate solid electrolyte material is subjected to nanocrystallization through sanding;
2. the nano phosphate solid electrolyte material passes through a coating machine to be mixed with a positive ternary material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Coating, heating the coated material to 850 ℃ at the speed of 5 ℃/min, preserving the heat for 8 hours, and naturally cooling to obtain the phosphate solid electrolyte material coated anode material;
3. electrochemical test As in example 1
The sixth example is different from the second example in that the dry mixing device is used in the present example. The test results are shown in Table 1
Example 7
In contrast to example 1, this example used LiNi 0.83 Co 0.1 Mn 0.07 O 2 And coating the ternary cathode material.
Example 8
In contrast to example 2, this example used LiNi 0.83 Co 0.1 Mn 0.07 O 2 And coating the ternary cathode material.
Example 9
In contrast to example 3, this example used LiNi 0.83 Co 0.1 Mn 0.07 O 2 And coating the ternary cathode material.
Example 10
In contrast to example 4, this example used LiNi 0.83 Co 0.1 Mn 0.07 O 2 And coating the ternary cathode material.
Example 11
In contrast to example 5, this example used LiNi 0.83 Co 0.1 Mn 0.07 O 2 And coating the ternary cathode material.
Example 12
In contrast to example 6, this example used LiNi 0.83 Co 0.1 Mn 0.07 O 2 And coating the ternary cathode material.
Comparative example 1
Through sanding, the AlPO is ground 4 The nano-sized material is processed by a coating machine to obtain nano-sized AlPO 4 LiNi and anode ternary material 0.8 Co 0.1 Mn 0.1 O 2 Coating is carried out; heating the coated material to 900 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and naturally cooling to obtain AlPO 4 @NCM811。
Comparative example 2
Through sanding, the LATP material is nanocrystallized, and through a coating machine, the nanocrystallized LATP and the anode ternary material LiNi are 0.8 Co 0.1 Mn 0.1 O 2 Coating is carried out; heating the coated material to 900 ℃ at a speed of 3 ℃/min, preserving the heat for 12h, and naturally cooling to obtain the LATP @ NCM811.
Comparative example 3
By sanding, liTiOPO 4 The material is nanocrystallized, and the nanocrystallized LiTiOPO is processed by a coating machine 4 LiNi and anode ternary material 0.8 Co 0.1 Mn 0.1 O 2 Coating is carried out; heating the coated material to 5 ℃/minKeeping the temperature at 950 ℃ for 8h, and naturally cooling to obtain the LiTiOPO 4 @NCM811。
Comparative example 4
Sanding Al 2 O 3 The material is nanocrystallized, and the nanocrystallized Al is processed by a coating machine 2 O 3 LiNi and anode ternary material 0.8 Co 0.1 Mn 0.1 O 2 Coating is carried out; heating the coated material to 950 ℃ at a speed of 5 ℃/min, preserving the heat for 8 hours, and naturally cooling to obtain Al 2 O 3 @NCM811。
Comparative example 5
90% of LATP, 5% of AlPO 4 、5%LiTiOPO 4 The material is directly mixed and nanocrystallized by sanding, and the nanocrystallized material and the anode ternary material LiNi are 0.8 Co 0.1 Mn 0.1 O 2 And (3) coating, heating the coated material to 800 ℃ at a speed of 5 ℃/min, preserving the heat for 6h, and naturally cooling to obtain the phosphate solid electrolyte material coated anode material.
The difference from embodiment 1 is that: the three materials of this comparative example were directly mixed, but heterogeneous three-phase materials.
Comparative example 6
1. Preparing materials:
1. according to LATP, alPO 4 、LiTiOPO 4 In this example, the ratio of LATP to AlPO is 60% 4 30% of LiTiOPO 4 The percentage is 10 percent, and a lithium source, a titanium source, a phosphorus source and an aluminum source are calculated according to the proportion; selection of LiOH. H 2 O as a lithium source, tiP 2 O 7 (titanium Pyrophosphate) as phosphorus and titanium Source, NH 4 H 2 PO 4 (monoammonium phosphate) as a supplemental phosphorus source, al (OH) 3 (aluminum hydroxide) as Al (OH) 3 (ii) a Weighing 39.445g LiOH. H 2 O，115.025g NH 4 H 2 PO 4 31.201g of aluminum hydroxide, 235.116g of TiP 2 O 7 Pouring the weighed powder into 1683.152g of water, wherein the mass of the powder accounts for 20% of the total mass of the slurry;
2. grinding the slurry for 12 hours by a stirring and grinding process, wherein the ball-to-feed ratio is 5 (the ball-to-feed ratio is the mass of grinding balls: the mass of powder), and weighing 3188.475g of zirconia balls with the diameter of 3 mm;
3. after grinding, drying the slurry at 120 ℃, drying to obtain powder agglomerated into a block, and grinding the powder through a 200-mesh screen by using a mortar;
4. grinding the sieved powder, placing the powder in an alumina crucible, heating to 950 ℃ at the speed of 2.5 ℃/min, preserving heat for 8 hours, and naturally cooling;
5. and taking out the cooled phosphate material, and grinding the phosphate material through a 200-mesh screen to obtain the phosphate solid electrolyte material.
2. Use 1-positive electrode coating
1. The phosphate solid electrolyte material is subjected to nanocrystallization through sanding;
2. the nano phosphate solid electrolyte material is coated with an anode ternary material NCM811 through a coating machine, the temperature of the coated material is raised to 900 ℃ at the rate of 3 ℃/min, the temperature is kept for 12h, and the anode material coated with the phosphate solid electrolyte material can be obtained after natural cooling;
the main difference of this comparative example compared with example 4 is that: alPO 4 Is not in the range (AlPO) 4 The range of (1) is 2 to 20%).
Comparative example 7
1. Preparing materials:
1. according to LATP, alPO 4 In this example, the ratio of LATP to AlPO is 80% 4 Calculating the lithium source, the titanium source, the phosphorus source and the aluminum source according to the proportion of 20 percent; selection of LiOH. H 2 O as a lithium source, NH 4 H 2 PO 4 (monoammonium phosphate) as phosphorus source, al 3 O 4 As an aluminum source, tiO 2 As a titanium source, 47.00g of LiOH. H was weighed 2 O， 345.08g NH 4 H 2 PO 4 ，26.51g Al 3 O 4 ，102.227g TiO 2 Pouring weighed powder into 1215.224g of water, wherein the mass of the powder accounts for 30% of the total mass of the slurry;
2. grinding the slurry for 12h by a sand grinding process, wherein the ball-to-feed ratio is 5 (the ball-to-feed ratio is the mass of grinding balls: the mass of powder), and weighing 3188.475g of zirconia balls with the diameter of 3mm.
3. After the grinding is completed, the slurry is dried at a temperature of 120 ℃. Drying to obtain agglomerated powder, and grinding the powder by using a mortar and sieving by using a 200-mesh sieve.
4. Grinding the sieved powder, placing the powder in an alumina crucible, heating to 950 ℃ at the speed of 2.5 ℃/min, preserving heat for 8 hours, and then naturally cooling.
5. And taking out the cooled phosphate material, and grinding the phosphate material through a 200-mesh screen to obtain the phosphate solid electrolyte material.
2. Use 1-positive electrode coating
1. The phosphate solid electrolyte material is subjected to nanocrystallization through sanding;
2. the nano phosphate solid electrolyte material is coated with an anode ternary material NCM811 through a coating machine, the temperature of the coated material is raised to 900 ℃ at the rate of 3 ℃/min, the temperature is kept for 12h, and the anode material coated with the phosphate solid electrolyte material can be obtained after natural cooling;
the main difference of this comparative example compared to example 1 is that: this embodiment has only LATP and AlPO 4 Does not contain LiTiOPO 4 。
Comparative example 8
1. Preparing materials:
1. according to LATP, liTiOPO 4 In this example, the ratio of LATP to LiTiOPO is 80% 4 Calculating the lithium source, the titanium source, the phosphorus source and the aluminum source according to the proportion of 20 percent; selection of LiOH. H 2 O as a lithium source, NH 4 H 2 PO 4 (monoammonium phosphate) as phosphorus source, al 3 O 4 (aluminum oxide) as aluminum source, tiO 2 (titanium dioxide) 55.391g of LiOH. H was weighed as a titanium source 2 O， 299.065g NH 4 H 2 PO 4 ， 16.314g Al 3 O 4 ，118.2g TiO 2 Pouring weighed powder into 1955.88g of water, wherein the mass of the powder accounts for 20 percent of the total mass of the slurry;
2. grinding the slurry for 12 hours by a sand grinding process, wherein the ball-to-feed ratio is 5 (the ball-to-feed ratio is the mass of grinding balls: the mass of powder), and weighing 3188.475g of zirconia balls with the diameter of 3 mm;
3. after grinding, drying the slurry at 120 ℃, drying to obtain powder agglomerated into a block, and grinding the powder through a 200-mesh screen by using a mortar;
4. grinding the sieved powder, placing the powder in an alumina crucible, heating to 950 ℃ at the speed of 2.5 ℃/min, preserving heat for 8 hours, and naturally cooling;
5. and taking out the cooled phosphate material, and grinding the phosphate material through a 200-mesh screen to obtain the phosphate solid electrolyte material.
2. Use 1-coating of positive electrode
1. Grinding the phosphate solid electrolyte material to be nano-sized;
2. the phosphate solid electrolyte material after the nanocrystallization passes through a coating machine to be mixed with a positive ternary material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Coating, heating the coated material to 900 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and naturally cooling to obtain the phosphate solid electrolyte material coated anode material;
the main difference of this comparative example compared to example 1 is that: this example only includes LATP and AlPO 4 Does not contain LiTiOPO 4 。
Comparative example 9
1. Preparing materials:
1. according to AlPO 4 、LiTiOPO 4 In this example, alPO 4 50% of LiTiOPO 4 50 percent, calculating a lithium source, a titanium source, a phosphorus source and an aluminum source according to the proportion; selection of LiOH. H 2 O as a lithium source, NH 4 H 2 PO 4 (monoammonium phosphate) as phosphorus source, al 3 O 4 (aluminum oxide) as aluminum source, tiO 2 (titanium dioxide) As a titanium source, 20.981g of LiOH. H were weighed 2 O，115.025g NH 4 H 2 PO 4 ，25.49g Al 3 O 4 ，39.93g TiO 2 Pouring weighed powder into 470g of water, wherein the weight of the powder accounts for 20 percent of the total weight of the slurry;
2. grinding the slurry for 12h by a sand grinding process, wherein 3357.15g of zirconia balls with the diameter of 3mm are weighed at a ball-to-feed ratio of 5 (the ball-to-feed ratio is the mass of grinding balls: the mass of powder);
3. after grinding, drying the slurry at 120 ℃, drying to obtain powder agglomerated into a block, and grinding the powder through a 200-mesh screen by using a mortar;
4. grinding the sieved powder, placing the powder in an alumina crucible, heating to 950 ℃ at the speed of 2.5 ℃/min, preserving heat for 8 hours, and naturally cooling;
5. and taking out the cooled phosphate material, and grinding the phosphate material through a 200-mesh screen to obtain the phosphate solid electrolyte material.
2. Use 1-coating of positive electrode
1. Grinding the phosphate solid electrolyte material to be nano-sized;
2. the phosphate solid electrolyte material after the nanocrystallization passes through a coating machine to be mixed with a positive ternary material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Coating, heating the coated material to 900 ℃ at a speed of 3 ℃/min, preserving heat for 12h, and naturally cooling to obtain the phosphate solid electrolyte material coated anode material;
the main difference of this comparative example compared to example 1 is that: this example has only LiTiOPO 4 、AlPO 4 And does not contain LATP.
Comparative example 10
This comparative example uses LiNi in comparison with comparative example 9 0.83 Co 0.1 Mn 0.07 O 2 Coating a ternary cathode material;
the electrical testing method adopted in the above comparative example is the same as that of the example, and the details of the application are not repeated.
TABLE 1 Table of data on electrical properties of examples and comparative examples for application of phosphate solid electrolyte materials
Figure 492788DEST_PATH_IMAGE001
As is clear from Table 1, the present invention was used in examples 1 to 6The phosphate material provided by the invention is LiNi as a ternary material of the anode and the cathode 0.8 Co 0.1 Mn 0.1 O 2 After the coating treatment, the discharge specific capacity is more than 185.4mAh/g, the first coulombic efficiency is more than 91.2%, the capacity retention rate is more than 63.9% after 100 cycles of 0.5C circulation, the 0.5C discharge specific capacity is more than 162.3mAh/g, and the 5C discharge specific capacity is more than 110.2 mAh/g. Examples 7 to 12 adopt the phosphate material provided by the present invention to a positive electrode ternary material LiNi 0.83 Co 0.1 Mn 0.07 O 2 After coating treatment, the discharge specific capacity is more than 191.9mAh/g, the first coulombic efficiency is more than 90.2%, the capacity retention rate is more than 64.0% after 100 cycles of 0.5C circulation, the 0.5C discharge specific capacity is more than 160.1mAh/g, and the 5C discharge specific capacity is more than 108.7 mAh/g.
According to the data, the phosphate material provided by the invention is either the coating anode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Or LiNi 0.83 Co 0.1 Mn 0.07 O 2 All show excellent electrochemical performance. Compared with the examples 1 to 12, the initial specific capacity, the coulombic efficiency and the capacity retention rate after 50 cycles of the comparative examples 1 to 10 are obviously reduced, and the electrochemical performance is deteriorated.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The phosphate material consists of titanium aluminum lithium phosphate, aluminum phosphate and titanium lithium oxygen phosphate, wherein the content of the titanium aluminum lithium phosphate is 50-95wt%, the content of the aluminum phosphate is 2-20wt%, and the content of the titanium lithium oxygen phosphate is 2-30wt%.
2. The phosphate material according to claim 1, wherein the content of lithium titanium aluminum phosphate is 65 to 90wt%, the content of aluminum phosphate is 2.5 to 15wt%, and the content of lithium titanium oxide phosphate is 2.5 to 20wt%.
3. The method of preparing the phosphate material of claim 1, comprising the steps of:
a) According to the proportion of the phosphate material of claim 1, carrying out dry mixing or wet mixing on a lithium source, a titanium source, a phosphorus source and an aluminum source to obtain mixed powder;
b) And sintering the mixed powder to obtain the phosphate material.
4. The preparation method according to claim 3, wherein the dry mixing is specifically:
and (3) mixing the lithium source, the titanium source, the phosphorus source and the aluminum source in a high-speed mixer, a vertical mixer or a double helix conical mixer for 10 to 90min.
5. The preparation method according to claim 3, wherein the wet mixing is specifically:
mixing a lithium source, a titanium source, a phosphorus source and an aluminum source in a solvent to obtain slurry;
and (3) carrying out planetary ball milling, stirring milling or sand milling on the slurry for 3-6 h, drying at 100-150 ℃, and then grinding and sieving.
6. The preparation method according to claim 5, wherein the content of the powder in the slurry is 15 to 45wt%.
7. The preparation method according to claim 3, wherein the temperature rise speed of the sintering is 2 to 5 ℃/min, the temperature of the sintering is 500 to 1500 ℃, and the time is 6 to 12h.
8. The production method according to any one of claims 3 to 7, wherein the lithium source is selected from one or more of lithium carbonate, lithium hydroxide, lithium phosphate, lithium dihydrogen phosphate, lithium acetate and lithium nitrate, the titanium source is selected from one or more of titanium dioxide, titanium pyrophosphate and titanium phosphate, and the phosphorus source is selected from ammonium dihydrogen phosphate; the aluminum source is one or two selected from aluminum hydroxide and aluminum oxide.
9. A lithium ion battery, which comprises a positive electrode, a negative electrode and a solid electrolyte, and is characterized in that the solid electrolyte is selected from the phosphate material according to any one of claims 1 to 2 or the phosphate material prepared by the preparation method according to any one of claims 3 to 8.
10. The lithium ion battery of claim 9, wherein the positive electrode is of a material such as LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.8 and less than 0.9, and y is more than 0 and less than or equal to 0.1.
CN202211315308.6A 2022-10-26 2022-10-26 Phosphate material and lithium ion battery Pending CN115377485A (en)

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