CN116169247A - Prussian blue analogue coated solid-state battery positive electrode material and preparation method thereof - Google Patents
Prussian blue analogue coated solid-state battery positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The present specification discloses a Prussian blue analog coated solid state battery positive electrode material and a preparation method thereof, wherein the solid state battery positive electrode material comprises a positive electrode active material and a coating layer; the positive electrode active material is an oxide containing Li; the coating layer is Prussian blue analogues with cubic framework crystal structures; the Prussian blue analogue coating layer has a molecular structural formula A x M 1 [M 2 (CN) 6 ] y The method comprises the steps of carrying out a first treatment on the surface of the Wherein, A is alkali metal element; in the cubic frame crystal structure, metal atoms M 1 And M 2 Alternately occupying 8 vertices of the cube; metal atom M 1 And M 2 Between which are locatedThe CN triple bonds formed by the C atoms and the N atoms are connected, and the CN triple bonds are positioned on 12 edges of the cube; the a ion is located at the body centered position of the cube. The invention fundamentally solves the problems of large polarization effect, slow diffusion rate of lithium ions, poor multiplying power performance, short cycle life and the like of the solid-state battery.
Description
Technical Field
One or more embodiments of the present disclosure relate to the field of solid-state technologies, and in particular, to a Prussian blue analog coated solid-state battery positive electrode material and a preparation method thereof.
Background
Due to the advantages of high energy density, long cycle life and the like, lithium ion batteries are widely applied to various aspects of daily life of people at present, such as portable consumer electronic products, new energy automobiles, power grid energy storage and the like. However, the lithium ion battery is susceptible to thermal runaway during charge and discharge. After a certain temperature is exceeded, the flammable organic electrolyte in the battery fires and burns, which ultimately results in a great safety risk for the lithium ion battery. In order to solve the above-mentioned safety problem, it has been proposed to form a solid-state battery by replacing an organic liquid electrolyte in a lithium ion battery with a solid-state electrolyte. The melting point, boiling point and decomposition temperature of the solid electrolyte are far higher than those of the organic liquid electrolyte, so that the problem of safety performance of the battery can be solved to a great extent. Currently, three types of solid electrolyte chemical components are classified into sulfide, oxide and polymer in the solid state battery technology. The sulfide has the highest room-temperature ion conductivity, and can provide good lithium ion conductivity for the solid-state battery; in addition, the sulfide solid electrolyte has the characteristics of easy processing and the like, and is recognized as a solid battery technical route with the most extensive and large-scale prospect.
In a sulfide solid state batteryThe positive electrode part mainly comprises an oxide positive electrode active material, a sulfide solid electrolyte, a binder, a conductive auxiliary agent and the like. The oxide positive electrode active material is separated from the sulfide solid state electrolyte material by a "solid-solid" interface, as shown in fig. 1. Because the chemical potentials of the oxide and the sulfide on lithium ions are greatly different, the attraction of oxygen in the oxide positive electrode material on lithium ions Li+ is greater than that of sulfur in the sulfide electrolyte, so that a large amount of Li+ migrates to the positive electrode active material, lithium is poor at the side of a solid-solid interface close to the sulfide solid-state electrolyte, lithium is rich at the side of the solid-solid interface close to the oxide positive electrode material, a space charge layer is formed, and finally, a very large interface impedance is formed between the positive electrode material and the sulfide solid-state electrolyte, as shown in fig. 2. Interface resistance caused by the space charge layer is generally considered to be a main cause of defects such as poor rate performance, short cycle life, and the like of the solid-state battery. To solve this problem, dielectric nano BaTiO has been used 3 The material as a solid-solid interface buffer layer eliminates LiCoO 2 Positive electrode material and Li 6 PS 5 Space charge layers between Cl solid electrolytes (In-situ visualization ofthe space-charge-layer effect on interfacial lithium-ion transport In all-solid-state batteries, nature Communication, 11,5889 (2020)).
The Chinese patent application CN103633329A provides an all-solid-state lithium ion battery composite positive electrode material, which comprises a positive electrode active material and a coating layer arranged on the surface of the positive electrode active material, wherein the positive electrode active material is one or more of lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate, lithium nickel cobalt manganate, vanadium pentoxide, molybdenum trioxide and titanium disulfide, the coating layer is one or more lithium-containing transition metal oxides, the coating layer can effectively inhibit the formation of a space charge layer, an electrode/inorganic solid electrolyte interface is improved, the interface resistance of the all-solid-state lithium ion battery is reduced, and the cycle stability and durability of the all-solid-state battery are improved.
Chinese patent application CN111628158A provides a double-coated positive electrode material, a method for preparing the same, a battery sheet and a solid-state battery. The double-coated positive electrode materialThe material comprises a first coating layer and a second coating layer which are sequentially coated on a positive electrode material, wherein the positive electrode material comprises Li a Ni x Co y Mn 1-x-y O 2 Wherein x is more than 0.3 and less than 0.9, y is more than 0.1 and less than 0.35, a is more than 0.95 and less than 1.03, the first coating layer and the second coating layer are different, the first coating layer is a LATP layer or an LNTO layer, and the second coating layer is an LNTO layer or an LATP layer. The LATP and LNTO coating materials in the double-coated positive electrode material have a synergistic effect, the coating layer is firmly combined with the surface of the positive electrode material, the interface side reaction is well relieved, and the problem of polarization increase is further reduced; the potential difference of the interface layer is reduced to a greater extent, so that the interface impedance is reduced, and the problems of rapid capacity decay and excessive side reactions are alleviated.
The Chinese patent application CN113353988A discloses a lithium ion battery anode material which is of a core-shell structure and comprises a core layer and a shell layer coated on the surface of the core layer, wherein the core layer is Nb modified lithium cobalt oxide, so that the problem of particle breakage can be effectively solved in the charge and discharge process, and the diffusion rate of lithium ions in the lithium cobalt oxide can be improved; the shell layer is a metal oxide containing Nb, has a cubic phase structure and higher lithium ion conductivity, and can improve the problem of large internal resistance of interface contact between the positive electrode material and the solid electrolyte, thereby improving the electrochemical performance of the positive electrode material.
All three patents establish a buffer layer on the surface of the active material of the positive electrode material in a coating manner, so that the buffer layer is expected to solve the problem of an interface charge layer between oxide and sulfide. However, the buffer layers disclosed in the above three patents are all oxide materials, so the problem of solid-solid interface space charge layer between oxide and sulfide is not solved basically.
Chinese patent application CN110911634a discloses a positive electrode material and a method for preparing the same. The positive electrode material comprises a positive electrode active substance and fluorinated TiS coated on the positive electrode active substance 2 A material. The invention adopts fluorinated TiS 2 The material coats the positive electrode active material, so that the phenomenon of element interdiffusion with the positive electrode material in the preparation process can be relieved. However, this patent uses a solid phase mixing methodCoating, the surface of the positive electrode active material cannot be uniformly coated. In addition, the anode active material and the coating layer are required to be heated to the high temperature of 800 ℃ together for reaction in the coating process, so that the process flow and the manufacturing cost are increased.
Disclosure of Invention
In view of this, it is an object of one or more embodiments of the present specification to provide a Prussian blue analog coated solid state battery positive electrode material. The solid-state battery anode material of the invention is coated with a layer of Prussian blue analogues, so that the oxide active substance is not in direct contact with the sulfide solid-state electrolyte; prussian blue analogues with special crystal structures play a role of a buffer layer and successfully inhibit a space charge layer generated by a solid-solid interface in a solid-state battery, so that the problems of large polarization effect, low lithium ion diffusion rate, poor rate capability, short cycle life and the like of the solid-state battery are fundamentally solved.
A second object of the present specification is to provide a method for preparing the above-mentioned prussian blue analog-coated solid-state battery cathode material.
Based on the first item, the present specification provides the following technical solutions:
a Prussian blue analog coated solid-state battery positive electrode material comprises a positive electrode active substance and a coating layer;
the positive electrode active material is an oxide containing Li;
the coating layer is Prussian blue analogues with cubic framework crystal structures;
the Prussian blue analogue coating layer has a molecular structural formula A x M 1 [M 2 (CN) 6 ] y The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the liquid crystal display device comprises a liquid crystal display device,
the A is alkali metal element;
the M is 1 And M 2 Selected from one of metal elements Ti, V, cr, mn, fe, co, ni, cu, zn, M 1 And M 2 May be the same or different;
wherein x is more than or equal to 0 and less than or equal to 2; y is more than or equal to 0.75 and less than or equal to 1;
cubes of Prussian blue analoguesIn the crystal structure of the shape frame, metal atoms M 1 And M 2 Alternately occupying 8 vertices of the cube; metal atom M 1 And M 2 The three-dimensional cubic prism is connected by a CN triple bond formed by C atoms and N atoms, and the CN triple bond is positioned on 12 edges of the cubic prism; the a ion is located at the body centered position of the cube.
As one embodiment, the Li-containing oxide includes, but is not limited to, ternary layered oxide Li (Ni x Co y Mn z )O 2 、Li(Ni x Co y Al z )O 2 Lithium cobaltate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate or lithium-rich manganese; the Li (Ni) x Co y Mn z )O 2 And Li (Ni) x Co y Al z )O 2 X is more than or equal to 1/3 and less than or equal to 1; y is more than or equal to 0 and less than or equal to 1; z is more than or equal to 0 and less than or equal to 0.3;
as one embodiment, the alkali metal element is one of Li, na, and K.
Based on the second item, the present specification provides the following technical scheme:
the preparation method of the Prussian blue analog coated solid-state battery positive electrode material comprises the following steps of:
1) Weighing metal chloride, and dissolving the metal chloride in an alkali metal chloride saturated aqueous solution to obtain a solution A; weighed Na 4 M(CN) 6 Dissolving in alkali chloride saturated water solution to obtain solution B;
2) Adding the positive electrode active material into the solution A and uniformly stirring to obtain a solution C;
3) Dropping the solution B into the solution C, and adding metal chloride and Na 4 M(CN) 6 Generating a Prussian blue analogue surface coating layer on the surface of the positive electrode active material particles through a precipitation chemical reaction;
4) When metal chloride and Na 4 M(CN) 6 After the reaction is finished, filtering the suspension after the reaction to obtain solid particles; and (3) drying the obtained solid particles at low temperature to obtain the Prussian blue analog coated solid battery anode material.
As one embodiment, the metal is chlorinatedThe product being TiCl 2 、VCl 2 、CrCl 2 、MnCl 2 、FeCl 2 、CoCl 2 、NiCl 2 、CuCl 2 、ZnCl 2 One of the following; the concentration of the metal chloride in the solution A is 0.1-10mol/L.
As one embodiment, the Na 4 M(CN) 6 M of (C) is selected from Ti, V, cr, mn, fe, co, ni, cu or Zn.
As an embodiment, in step 1), the alkali metal chloride is one of LiCl, naCl, KCl.
In one embodiment, in step 1), the metal chloride is mixed with Na 4 M(CN) 6 The molar ratio of (2) is 0.1-10:1.
in a preferred embodiment, in step 1), the metal chloride is mixed with Na 4 M(CN) 6 The molar ratio of (2) is 0.5-2:1.
as an embodiment, in step 2), the positive electrode active material includes, but is not limited to, ternary layered oxide materials, such as Li (Ni x Co y Mn z )O 2 、Li(Ni x Co y Al z )O 2 Lithium cobaltate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate or lithium-rich manganese.
As an embodiment, in step 2), the solid content of the positive electrode active material in the solution C is 10% to 60%.
In one embodiment, in step 2), the molar ratio of the positive electrode active material to the metal chloride in the solution a is 1:0.001-0.05.
As an embodiment, in step 3), the volume ratio of the solution B to the solution C is 1: (0.1-10).
As an embodiment, in step 3), the precipitation chemistry is at a temperature of 25-99 ℃.
In a preferred embodiment, in step 3), the precipitation chemistry is carried out at a temperature of 50-70 ℃.
In one embodiment, in step 4), the low temperature drying temperature is 80-110 ℃.
Any range recited in the invention includes any numerical value between the endpoints and any sub-range of any numerical value between the endpoints or any numerical value between the endpoints.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a solid-state battery anode material coated by Prussian blue analogues, wherein the anode active material is an oxide anode material, such as ternary material, lithium cobaltate material, lithium iron phosphate material, lithium manganate material, lithium-rich manganese material and the like; coating the particle surface of the oxide positive electrode active material with a Prussian blue analogue with a cube crystal structure, wherein the Prussian blue analogue contains alkali metal ions, and when the alkali metal ions deviate from the cube center position, the Prussian blue analogue can generate a space polarization phenomenon, so that a space charge layer generated when the oxide positive electrode active material is directly contacted with sulfide solid electrolyte is eliminated; the buffer layer of Prussian blue analog is provided, so that the problems of large battery polarization, poor multiplying power, short service life and the like caused by the space charge layer are successfully solved.
Drawings
FIG. 1 is a schematic diagram of a solid interface structure of a conventional oxide positive electrode active material and a sulfide solid electrolyte;
FIG. 2 is a schematic diagram of a solid interface space charge layer of a prior oxide positive electrode active material in contact with a sulfide solid state electrolyte;
FIG. 3 is a schematic diagram of the frame crystal structure of the Prussian blue analogues of the coating layer obtained in example 1;
FIG. 4 is a schematic diagram showing a buffer layer of Prussian blue analogues obtained in example 1 for solving the problem of space charge layer;
FIG. 5 is an X-ray diffraction chart of the coating material obtained in example 1.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the following specific examples.
It is noted that unless otherwise defined, technical or scientific terms used in one or more embodiments of the present disclosure should be taken in a general sense as understood by one of ordinary skill in the art to which the present disclosure pertains. The use of the terms "first," "second," and the like in one or more embodiments of the present description does not denote any order, quantity, or importance, but rather the terms "first," "second," and the like are used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof, but does not exclude other elements or items.
In the invention, the raw materials are as follows:
Na 4 M(CN) 6 ，Li(Ni x Co y Mn z )O 2 ，Li(Ni x Co y Al z )O 2 lithium cobaltate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate, lithium-rich manganese and the like are all purchased from an Aba Ding Shiji net;
unless otherwise indicated, all starting materials herein are commercially available, and the equipment used in the present invention may be conventional in the art or may be conventional in the art.
As one aspect of the present invention, a Prussian blue analog coated solid state battery positive electrode material of the present invention includes a positive electrode active material and a coating layer;
the positive electrode active material is an oxide containing Li;
the coating layer is Prussian blue analogues with cubic framework crystal structures;
the Prussian blue analogue coating layer has a molecular structural formula A x M 1 [M 2 (CN) 6 ] y The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the liquid crystal display device comprises a liquid crystal display device,
the A is alkali metal element;
the M is 1 And M 2 Selected from one of metal elements Ti, V, cr, mn, fe, co, ni, cu, zn, M 1 And M 2 May be the same or different;
wherein x is more than or equal to 0 and less than or equal to 2; y is more than or equal to 0.75 and less than or equal to 1;
in the cubic framework crystal structure of Prussian blue analogues, the metal atom M 1 And M 2 Alternately occupying 8 vertices of the cube; metal atom M 1 And M 2 The three-dimensional cubic prism is connected by a CN triple bond formed by C atoms and N atoms, and the CN triple bond is positioned on 12 edges of the cubic prism; the a ion is located at the body centered position of the cube.
As one embodiment, the Li-containing oxide includes, but is not limited to, ternary layered oxide Li (Ni x Co y Mn z )O 2 、Li(Ni x Co y Al z )O 2 Lithium cobaltate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate or lithium-rich manganese; the Li (Ni) x Co y Mn z )O 2 And Li (Ni) x Co y Al z )O 2 X is more than or equal to 1/3 and less than or equal to 1; y is more than or equal to 0 and less than or equal to 1; z is more than or equal to 0 and less than or equal to 0.3;
as one embodiment, the alkali metal element is one of Li, na, and K.
As another aspect of the present invention, the preparation method of the solid-state battery cathode material coated with the prussian blue analog of the present invention includes the following steps:
1) Weighing metal chloride, and dissolving the metal chloride in an alkali metal chloride saturated aqueous solution to obtain a solution A; weighed Na 4 M(CN) 6 Dissolving in alkali chloride saturated water solution to obtain solution B;
2) Adding the positive electrode active material into the solution A and uniformly stirring to obtain a solution C;
3) Dropping the solution B into the solution C, and adding metal chloride and Na 4 M(CN) 6 Generating a Prussian blue analogue surface coating layer on the surface of the positive electrode active material particles through a precipitation chemical reaction;
4) When metal chloride and Na 4 M(CN) 6 After the reaction is finished, filtering the suspension after the reaction to obtain solid particles; and (3) drying the obtained solid particles at low temperature to obtain the Prussian blue analog coated solid battery anode material.
According to some embodiments of the inventionFor example, the metal chloride is TiCl 2 、VCl 2 、CrCl 2 、MnCl 2 、FeCl 2 、CoCl 2 、NiCl 2 、CuCl 2 、ZnCl 2 One of the following; the concentration of the metal chloride in the solution A is 0.1-10mol/L.
According to some embodiments of the invention, the Na 4 M(CN) 6 M of (C) is selected from Ti, V, cr, mn, fe, co, ni, cu or Zn.
According to certain embodiments of the invention, in step 1), the alkali chloride is one of LiCl, naCl, KCl.
According to certain embodiments of the invention, in step 1), the metal chloride is mixed with Na 4 M(CN) 6 The molar ratio of (2) is 0.1-10:1.
according to certain embodiments of the invention, in step 1), the metal chloride is mixed with Na 4 M(CN) 6 The molar ratio of (2) is 0.5-2:1.
according to certain embodiments of the present invention, in step 2), the positive electrode active material includes, but is not limited to, ternary layered oxide materials, such as Li (Ni x Co y Mn z )O 2 、Li(Ni x Co y Al z )O 2 Lithium cobaltate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate or lithium-rich manganese.
According to certain embodiments of the invention, in step 2), the solid content of the positive electrode active material in the solution C is 10% -60%.
According to certain embodiments of the invention, in step 2), the molar ratio of the positive electrode active material to the metal chloride in solution a is 1:0.001-0.05.
According to certain embodiments of the invention, in step 3), the volume ratio of the solution B to the solution C is 1:0.1-10, including but not limited to 1:0.1-9, 1:0.1-8, 1:0.1-7, 1:0.1-6, 1:0.1-5, 1:0.1-4, 1:0.1-3, 1:0.1-2, 1:0.1-1, 1:1-9, 1:1-8, 1:1-7, 1:1-6, 1:1-5, 1:1-4, 1:1-3, 1:1-2, 1:2-9, 1:2-8, 1:2-7, 1:2-6, 1:2-5, 1:2-4, 1:2-3, 1:3-9, 1:3-8, 1:3-7, 1:3-6, 1:3-5, 1:3-4, 1:4-9, 1:4-8, 1:4-7, 1:4-6, 1:4-5, 1:5-9, 1:5-8, 1:5-7, 1:5-6, 1:6-9, 1:6-8, 1:6-7.
According to certain embodiments of the invention, in step 3), the precipitation chemistry is at a temperature of 25-99 ℃.
According to certain embodiments of the invention, in step 3), the precipitation chemistry is at a temperature of 50-70 ℃.
According to certain embodiments of the invention, in step 4), the low temperature drying temperature is 80-110 ℃.
Example 1
The preparation method of the Prussian blue analog coated solid-state battery positive electrode material comprises the following steps of:
1) Weighing 4mmol FeCl at 25deg.C 2 Dissolving in 40ml of LiCl saturated aqueous solution, and uniformly stirring to obtain solution A; weigh 2mmol Na 4 Fe(CN) 6 Dissolving in 80ml of LiCl saturated aqueous solution, and uniformly stirring to obtain solution B;
2) 20g of ternary cathode material Li (Ni) 0.8 Co 0.1 Mn 0.1 )O 2 Putting the mixture into the solution A which is just obtained and continuously stirring the mixture;
3) Under nitrogen N 2 Dropwise adding the solution B into the turbid solution of the solution A and the positive electrode material at the temperature of 60 ℃ under the protection condition, and continuously stirring; during the dropping process, prussian blue analogues gradually form on the surface of the ternary cathode material particles.
4) After the solution B is completely dripped, continuously stirring the obtained suspension for 4 hours at 60 ℃ under the protection of nitrogen; filtering the suspension to obtain solid particles. And finally, drying the obtained solid particles for 12 hours at the temperature of 80 ℃ to obtain the Prussian blue analog coated solid battery anode material.
And (3) detecting:
FIG. 3 is a schematic diagram of the frame crystal structure of Prussian blue analogues of the coating layer obtained in this example;
fig. 4 is a schematic diagram of a buffer layer of prussian blue analog obtained in this embodiment for solving the problem of space charge layer.
Examples 2 to 10
Except for FeCl according to Table 1 2 Concentration of Na 4 Fe(CN) 6 The concentrations, the mass of ternary material added to solution A, and the reaction temperatures of step 3 and step 4 were the same as in example 1, see Table 1 below.
Comparative examples 1 to 3
Except that FeCl is not added 2 And Na (Na) 4 Fe(CN) 6 Other synthesis conditions were the same as in example 1 except for the reaction temperatures in step 3 and step 4, as shown in Table 1 below:
table 1:
the positive electrode sheets fabricated in examples 1 to 10 and comparative examples 1 to 3 were assembled into a simulated battery, and the interface resistance, charge-discharge capacity test, rate performance test, etc. were performed on the battery, and the test results are shown in table 2 below.
Simulation of battery assembly:
the positive electrode plate, li 6 PS 5 The Cl electrode layer, and the Li-In alloy negative electrode are assembled into an all-solid-state secondary battery.
Interface impedance, charge-discharge capacity, rate performance test:
and placing the assembled all-solid-state secondary battery into a pressurizing jacket capable of maintaining pressure, and performing battery impedance test at the pressure of 300Mpa, wherein the test frequency is 3.5MHz-0.1Hz. The all-solid-state secondary battery was then subjected to charge-discharge test with a current density of 20mA/g, and a cut-off voltage of 1.9 to 3.7V. After one charge-discharge cycle, the current density is increased to 200mA/g for multiplying power performance test, and the ratio of the specific discharge capacity obtained under the condition of 200mA/g to the specific discharge capacity obtained under the condition of 20mA/g is the multiplying power capacity retention rate.
The test data for the positive electrode sheets obtained in examples 1 to 10 and comparative examples 1 to 3 are summarized in Table 2 below.
Table 2:
| sequence number | Interface impedance (omega) | Discharge capacity (mAh/g) | Rate capacity retention (%) |
| Example 1 | 49.1 | 193.3 | 87.2 |
| Example 2 | 60.3 | 182.5 | 84.3 |
| Example 3 | 77.2 | 178.2 | 77.2 |
| Example 4 | 72.3 | 180.6 | 80.6 |
| Example 5 | 66.4 | 181.5 | 79.3 |
| Example 6 | 83.2 | 169.6 | 74.8 |
| Example 7 | 103.5 | 154.5 | 70.4 |
| Example 8 | 88.2 | 166.3 | 71.0 |
| Example 9 | 76.3 | 176.2 | 76.5 |
| Example 10 | 53.1 | 188.2 | 84.3 |
| Comparative example 1 | 166.2 | 148.9 | 68.3 |
| Comparative example 2 | 229.4 | 138.4 | 50.3 |
| Comparative example 3 | 179.8 | 141.1 | 71.9 |
As can be seen from table 2:
1) The positive electrode materials in examples 1 to 10 had an impedance maximum of only 103.5 Ω after having been coated with the prussian blue analog;
2) The positive electrode materials in comparative examples 1 to 3 did not have a prussian blue analog coating layer, and the minimum impedance was 166.2 Ω only;
3) Therefore, when the positive electrode material coats the Prussian blue analog of the present invention, the impedance is reduced by approximately 40%.
From the above, it can be seen that: the assembled battery coated with the positive electrode material by the Prussian blue analog provided by the invention has low interface impedance and excellent charge-discharge capacity and rate capability.
The Prussian blue analog coated positive electrode material has the advantages of simple composition, easily obtained raw materials, simple manufacturing method and excellent product consistency, and can solve the problem of space charge layer of the solid interface between the solid state battery positive electrode active material and the solid state electrolyte.
The foregoing describes specific embodiments of the present disclosure. Other embodiments are within the scope of the following claims. In some cases, the actions or steps recited in the claims can be performed in a different order than in the embodiments and still achieve desirable results. In addition, the processes depicted in the specification do not necessarily require the particular order shown, or sequential order, to achieve desirable results. In some embodiments, multitasking and parallel processing are also possible or may be advantageous.
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the disclosure, including the claims, is limited to these examples; combinations of features of the above embodiments or in different embodiments are also possible within the spirit of the present disclosure, steps may be implemented in any order, and there are many other variations of the different aspects of one or more embodiments described above which are not provided in detail for the sake of brevity.
Furthermore, where specific details are set forth in order to describe example embodiments of the disclosure, it should be apparent to one skilled in the art that one or more embodiments of the disclosure can be practiced without, or with variation of, these specific details. Accordingly, the description is to be regarded as illustrative in nature and not as restrictive.
While the present disclosure has been described in conjunction with specific embodiments thereof, many alternatives, modifications, and variations of those embodiments will be apparent to those skilled in the art in light of the foregoing description.
The present disclosure is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Any omissions, modifications, equivalents, improvements, and the like, which are within the spirit and principles of the one or more embodiments of the disclosure, are therefore intended to be included within the scope of the disclosure.
Claims (10)
1. A Prussian blue analog coated solid-state battery positive electrode material comprises a positive electrode active substance and a coating layer; the method is characterized in that:
the positive electrode active material is an oxide containing Li;
the coating layer is Prussian blue analogues with cubic framework crystal structures;
the Prussian blue analogue coating layer has a molecular structural formula A x M 1 [M 2 (CN) 6 ] y The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the liquid crystal display device comprises a liquid crystal display device,
the A is alkali metal element;
the M is 1 And M 2 Selected from one of metal elements Ti, V, cr, mn, fe, co, ni, cu, zn, M 1 And M 2 May be the same or different;
wherein x is more than or equal to 0 and less than or equal to 2; y is more than or equal to 0.75 and less than or equal to 1;
in the cubic framework crystal structure of Prussian blue analogues, the metal atom M 1 And M 2 Alternately occupying 8 vertices of the cube; metal atom M 1 And M 2 The three-dimensional cubic prism is connected by a CN triple bond formed by C atoms and N atoms, and the CN triple bond is positioned on 12 edges of the cubic prism; the a ion is located at the body centered position of the cube.
2. The prussian blue analog coated solid state battery positive electrode material according to claim 1, wherein: the Li-containing oxide includes, but is not limited to, ternary layered oxide Li (Ni x Co y Mn z )O 2 、Li(Ni x Co y Al z )O 2 Lithium cobaltate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate or lithium-rich manganese; the Li (Ni) x Co y Mn z )O 2 And Li (Ni) x Co y Al z )O 2 X is more than or equal to 1/3 and less than or equal to 1; y is more than or equal to 0 and less than or equal to 1; z is more than or equal to 0 and less than or equal to 0.3.
3. The prussian blue analog coated solid state battery positive electrode material according to claim 1, wherein: the alkali metal element is one of Li, na and K.
4. A method for preparing the Prussian blue analog coated solid state battery positive electrode material according to any one of claims 1 to 3, comprising the steps of:
1) Weighing metal chloride, and dissolving the metal chloride in an alkali metal chloride saturated aqueous solution to obtain a solution A; weighed Na 4 M(CN) 6 Dissolving in alkali chloride saturated water solution to obtain solution B;
2) Adding the positive electrode active material into the solution A and uniformly stirring to obtain a solution C;
3) Dropping the solution B into the solution C, and adding metal chloride and Na 4 M(CN) 6 Generating a Prussian blue analogue surface coating layer on the surface of the positive electrode active material particles through a precipitation chemical reaction;
4) When metal chlorideNa 4 M(CN) 6 After the reaction is finished, filtering the suspension after the reaction to obtain solid particles; and (3) drying the obtained solid particles at low temperature to obtain the Prussian blue analog coated solid battery anode material.
5. The method of claim 4, wherein: the metal chloride is TiCl 2 、VCl 2 、CrCl 2 、MnCl 2 、FeCl 2 、CoCl 2 、NiCl 2 、CuCl 2 、ZnCl 2 One of the following; the concentration of the metal chloride in the solution A is 0.1-10mol/L.
6. The method of manufacturing according to claim 4, wherein: the Na is 4 M(CN) 6 M of (C) is selected from Ti, V, cr, mn, fe, co, ni, cu or Zn.
7. The method of manufacturing according to claim 4, wherein: in step 1), the alkali metal chloride is one of LiCl, naCl, KCl.
8. The method of manufacturing according to claim 4, wherein: in step 1), the metal chloride is mixed with Na 4 M(CN) 6 The molar ratio of (2) is 0.1-10:1.
9. the method of manufacturing according to claim 4, wherein: in step 1), the metal chloride is mixed with Na 4 M(CN) 6 The molar ratio of (2) is 0.5-2:1.
10. the method of manufacturing according to claim 4, wherein: in step 2), the positive electrode active material includes, but is not limited to, ternary layered oxide materials such as Li (Ni) x Co y Mn z )O 2 、Li(Ni x Co y Al z )O 2 Lithium cobaltate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate or lithium-rich manganese;
preferably, in the step 2), the solid content of the positive electrode active material in the solution C is 10% to 60%;
preferably, in the step 2), the molar ratio of the positive electrode active material to the metal chloride in the solution A is 1:0.001-0.05;
preferably, in step 3), the volume ratio of the solution B to the solution C is 1:0.1-10;
preferably, in step 3), the precipitation chemistry is at a temperature of 25-99 ℃;
preferably, in step 3), the precipitation chemistry is at a temperature of 50-70 ℃;
preferably, in step 4), the low temperature drying temperature is 80-110 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116345026A (en) * | 2023-05-31 | 2023-06-27 | 广汽埃安新能源汽车股份有限公司 | Battery core and battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116345026A (en) * | 2023-05-31 | 2023-06-27 | 广汽埃安新能源汽车股份有限公司 | Battery core and battery |
| CN116345026B (en) * | 2023-05-31 | 2023-08-15 | 广汽埃安新能源汽车股份有限公司 | Battery core and battery |
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