CN112038612A - Boron-doped & phosphite-coated nickel-based positive electrode material for lithium ion all-solid-state battery and preparation method thereof - Google Patents
Boron-doped & phosphite-coated nickel-based positive electrode material for lithium ion all-solid-state battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a boron-doped and phosphite-coated nickel-based positive electrode material for a lithium ion all-solid-state battery and a preparation method thereof. The characteristics of low melting point and high boiling point of the boron compound are utilized to promote the uniform distribution of the coating elements on the surface of the high-nickel anode material, so as to form a continuous and complete coating layer, namely a lithium ion conductor phosphate layer (LLP), and meanwhile, boron enters a material phase through high-temperature diffusion and is doped to play a role in stabilizing the material structure. The phosphite coating layer formed on the surface of the anode material can effectively improve the interface compatibility between the high-nickel anode material and the sulfide solid electrolyte, avoids the sharp increase of the interface impedance between the high-nickel anode material and the sulfide solid electrolyte caused by the space charge layer effect, and promotes the application of the high-nickel anode in the lithium ion sulfur-based electrolyte all-solid-state battery.
Description
The technical field is as follows:
the invention relates to the technical field of all-solid-state lithium ion battery materials and preparation thereof, in particular to a boron-doped and phosphite-coated co-modified high-nickel anode material for a sulfur-based solid electrolyte lithium ion battery, and preparation and application thereof.
Background art:
the lithium ion battery is widely applied to the field of mobile electronic products as an energy storage device, and is gradually expanded to the field of vehicles such as electric automobiles and the like; however, due to the rapid increase of the market demand of electric vehicles, higher requirements are also put on the energy density, cycle life and safety of power batteries, wherein positive and negative electrode materials, electrolytes and the like become hot spots for research. The traditional lithium ion battery takes a liquid organic ion conductive solvent as an electrolyte, has extremely poor stability at high temperature, is the weakest link of thermal runaway of the lithium ion battery in the working process, and cannot meet the development target of the power automobile battery with high energy density and high safety.
The replacement of conventional organic liquid electrolytes with solid electrolytes is the key to the next point of battery technology. Among the numerous lithium ion conductor solid-state electrolytes, sulfur-based solid-state electrolytes have very high lithium ion conductivity. However, sulfur-based solid electrolytes and the currently mainstream lithium ion battery layered lithium intercalation oxide positive electrode materials (LiNi)xN1-xO2，0.6≤x<1) The interface compatibility between the two materials is very poor, and a severe space charge layer effect exists, so that the ionic resistance between the positive electrode material and the sulfur-based solid electrolyte interface is large, the migration of lithium ions between the two material interfaces is limited, and the large-current charging and discharging are not facilitated.
In order to solve the problem of interface compatibility between the sulfur-based solid electrolyte and the layered lithium intercalation oxide cathode material, a buffer layer having good compatibility with both sulfide and the cathode material needs to be introduced at the interface of the two.
Phosphite compounds (LiLa)1-yMy(PO3)4Y is more than or equal to 0 and less than or equal to 0.4, abbreviated as LLP) has not gained much attention in the traditional lithium ion battery taking liquid organic electrolyte as a component because of the low electronic conductivity of the LLP. However, the phosphite compound LiLa1-yMy(PO3)4The polyanion compound has good interface compatibility with sulfur-based solid electrolyte and oxide cathode material at the same time, and the surface of the layered lithium-embedded oxide cathode material is coated with LiLa1-yMy(PO3)4The method avoids the sharp reduction of ionic conductance caused by the direct contact of the sulfur-based solid electrolyte and the oxide anode material, and can solve the problem of the interface between the sulfide solid electrolyte and the oxide anode material. Simultaneous phosphite compound LiLa1-yMy(PO3)4The lithium ion battery also has excellent chemical stability, electrochemical stability and high lithium ion conductivity, and can ensure the stability and safety of materials while solving the problem of interface stability of the materials.
In conclusion, the surface of the layered lithium-intercalated oxide cathode material is coated with LiLa1-yMy(PO3)4The method is beneficial to improving the stability of the interface and the lithium ion migration capacity, and provides a new technical route for the application of the high-energy, high-safety and high-rate sulfide solid-state battery.
The invention content is as follows:
the purpose of the invention is as follows: the boron-doped and phosphite-coated nickel-based positive electrode material for the lithium ion all-solid-state battery and the preparation method and application thereof are provided, so that the problem of interface compatibility between the high-nickel oxide positive electrode material of the lithium ion battery and a sulfur-based solid electrolyte is solved, and the high-nickel oxide positive electrode material and the sulfur-based solid electrolyte can be better applied to the solid lithium ion battery.
A boron-doped and phosphite-coated nickel-based positive electrode material for a lithium ion all-solid-state battery is composed of a boron-doped lithium ion battery nickel-based positive electrode material and a phosphite coating layer on the surface of the material. The particle size of the boron-doped lithium ion battery anode material is 1-100 mu m, and the thickness of the coating layer is 0.5-500 nm.
The boron doping for the lithium ion all-solid-state battery&In the phosphite-coated nickel-based positive electrode material, the nickel-based positive electrode material of the lithium ion battery is a layered positive electrode material, and the chemical composition of the nickel-based positive electrode material is LiNixN1-xO2，0.6≤x<1, N is any one of Co, Mn, Al, Zr, Cr and MgOne or more than one; the surface coating layer is polyanion phosphite LiLa1-yMy(PO3)4Y is more than or equal to 0 and less than or equal to 0.4, and M is any one or more of Co, Mn, Al, Cr, Zr and B.
The boron doping for the lithium ion all-solid-state battery&In the phosphite-coated nickel-based positive electrode material, the boron doping amount is 0.05-20 mol% of the nickel-based positive electrode material of the lithium ion battery, preferably 0.1-5 mol%, and more preferably 0.5-3 mol%. Boron is doped in the nickel-based positive electrode material structure of the lithium ion battery to comprise BO3 2-、BO5 4-One or both of the forms are present. The amount of the surface coating compound is 0.01-20%, preferably 0.1-10%, and more preferably 0.5-3% of the nickel-based positive electrode material of the lithium ion battery.
The preparation method of the boron-doped and phosphite-coated nickel-based anode material for the lithium ion all-solid-state battery,
respectively weighing a phosphorus source, a lanthanum source, a lithium source and a boron source according to a certain proportion, adding a dispersing agent into a ball milling tank for ball milling, then continuously ball milling the added precursor of the nickel-based positive electrode material of the lithium ion battery, taking out the uniformly stirred mixture and drying; and grinding the dried product uniformly, sieving, and calcining the powder to obtain the catalyst.
The preparation method of the boron-doped and phosphite-coated nickel-based positive electrode material for the lithium ion all-solid-state battery comprises the following steps of: the phosphorus source comprises: one or more of ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate and phosphoric acid, and the lanthanum source comprises: one or more of lanthanum hydroxide, lanthanum nitrate, lanthanum carbonate and lanthanum oxide; the lithium source includes: one or more of lithium hydroxide, lithium carbonate, lithium nitrate and lithium oxalate; the boron source includes: one or two of boric acid and boron oxide, wherein the dispersant comprises C, H, N, O element compound which is liquid at normal temperature, preferably glycol; the proportion of the dosage of the dispersant to the raw materials is 0.05-20 mol/L.
The preparation method of the boron-doped and phosphite-coated nickel-based anode material for the lithium ion all-solid-state battery comprises the following steps of: the molar ratio of P to La in the lanthanum source is 3-5: 1, boron source: the molar ratio of the precursor of the nickel-based positive electrode material of the lithium ion battery is 0.0005-0.3, and the molar ratio of the lithium source: the molar ratio of (0.25 multiplied by phosphorus source + lanthanum source + boron source + lithium ion battery nickel-based positive electrode material precursor) is 1-1.3, preferably 1.05-1.1.
According to the preparation method of the boron-doped and phosphite-coated nickel-based positive electrode material for the lithium ion all-solid battery, a phosphorus source, a lanthanum source, a lithium source and a boron source are added, and the rotation speed range of ball milling after a dispersing agent is 50-800rpm, preferably 200-500 rpm; the volume ratio of the raw material to the grinding balls is 0.1-10, preferably 0.3-3. The grinding time is controlled to be 2-48h, preferably 3-8 h; adding the nickel-based positive electrode material precursor of the lithium ion battery, and continuing to perform ball milling for 2-24h, preferably 3-8h at the rotating speed of 50-800rmp, preferably 100-300 rpm.
According to the preparation method of the boron-doped and phosphite-coated nickel-based positive electrode material for the lithium ion all-solid-state battery, the uniformly stirred mixture is taken out and then is placed in a forced air drying oven to be dried for 10-48 hours at the temperature of 60-200 ℃; grinding the dried product uniformly, and sieving with a sieve mesh number of 100-800 meshes; preferably 400-500 mesh.
The preparation method of the boron-doped and phosphite-coated nickel-based cathode material for the lithium ion all-solid-state battery comprises the following steps of calcining at 600 ℃ at the first stage, preferably at 550 ℃ at 450-.
The invention also provides the boron-doped and phosphite-coated nickel-based anode material for the lithium ion all-solid-state battery, or the application of the boron-doped and phosphite-coated nickel-based anode material for the lithium ion all-solid-state battery prepared by the preparation method in preparing the anode material for the all-solid-state lithium ion battery; in particular to the application of the positive electrode material for the sulfur-based solid electrolyte all-solid-state lithium ion battery.
The boron doping for the lithium ion all-solid-state battery&The solid electrolyte used in the solid lithium ion battery with the phosphite coated nickel-based positive electrode material comprises Li9.54Si1.74P1.44S11.7Cl0.3、Li7P3S11、Li10GeP2S12Any one of the above.
Compared with the existing material, the material of the invention has the following advantages and positive effects:
1) in the material synthesis process, the characteristics of low melting point and high boiling point of the boron compound are utilized to form a liquid phase in the high-temperature sintering process, so that other coating layer raw materials can be better diffused along with the liquid phase formed by boron at high temperature, and lanthanum ions, large-particle-size ions with slow diffusion rate at high temperature, can be uniformly distributed on the surface of the anode material to realize uniform coating; on the other hand, along with the diffusion in the high-temperature process, boron atoms are easy to diffuse into the bulk phase of the anode material due to small ionic radius, occupy the tetrahedral interstitial positions in the transition metal oxide crystal to form doping and form bonds with lattice oxygen, and therefore the structural stability of the material is improved.
2) In the process, the LLP-coated lithium ion battery oxide anode material is obtained by one-step firing by utilizing the characteristic that the synthesis temperature of the polyanion salt LLP of the coating layer is close to the synthesis temperature of the oxide anode, and the coating layer material has good lithium ion conductivity, chemical stability and electrochemical stability.
3) As polyanion compounds, the LLP coating layer has good compatibility to oxide cathode materials and sulfur-based solid electrolyte materials, and LLP can be used as a buffer layer between the LLP coating layer and the oxide cathode materials, so that the application of the LLP coating layer and the sulfur-based solid electrolyte materials in solid lithium ion batteries is promoted.
In conclusion, the invention can improve the defects of the anode material of the existing lithium ion battery, so that the anode material can be better applied to the all-solid-state battery.
Drawings
The high nickel positive electrode material for an all-solid-state lithium ion battery according to the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
In the invention, a material sample which is not modified is marked as NCM, a phosphite-coated material is LLP @ NCM, and a material which is modified by boron doping and LLP coating is B & LLP @ NCM.
FIG. 1 is an XRD pattern of NCM and B & LLP @ NCM prepared in comparative example 1 and example 1;
FIG. 2 is a graph showing TEM inspection results of materials of NCM, LLP @ NCM and B & LLP @ NCM prepared in comparative example 1, comparative example 2 and example 1;
a) NCM prepared for comparative example 1;
b) LLP @ NCM prepared for comparative example 2;
c) b & LLP @ NCM prepared in example 1;
FIG. 3 is a further enlarged high resolution TEM image of the B & LLP @ NCM prepared in example 1;
FIG. 4 is a graph of the results of the element distribution in the B & LLP @ NCM material prepared in example 1 by SEM cross-section and EDS mapping analysis;
FIG. 5 is a graph showing the results of charge and discharge tests performed on button solid state batteries assembled from materials of NCM, LLP @ NCM and B & LLP @ NCM prepared in comparative example 1, comparative example 2 and example 1;
FIG. 5a, cycle performance comparison;
fig. 5b, rate performance comparison.
Detailed Description
The invention is further illustrated by the following examples without restricting it.
Example 1
Respectively weighing 0.0024mol of ammonium hydrogen phosphate, 0.0006mol of lanthanum hydroxide, 0.0324mol of lithium hydroxide and 0.0003mol of boric acid into a 250mL ball milling tank filled with 20mL of ethylene glycol, adding 200g of zirconia grinding balls with the particle sizes of 8mm, 12mm and 15mm according to the mass ratio of 4:3:3, placing the ball milling tank on a ball mill, carrying out ball milling for 3h at the rotating speed of 500rmp, and then adding 0.03mol of Ni0.7Co0.15Mn0.15(OH)2The precursor is continuously ball-milled for 2h at the rotating speed of 100rmp, and the uniformly stirred mixture is taken out and then is dried for 24h at the temperature of 90 ℃ in a forced air drying oven. Placing the dried product in a mortar for grinding uniformly, sieving with a 400-mesh sieve, placing the powder in a tubular furnace for calcining at 450 ℃ for 6h, heating to 800 ℃ and calcining for 15h to obtain boron-doped product&LiLa(PO3)4(LLP) -coated LiNi0.7Co0.15Mn0.15O2And (3) a positive electrode material.
Comparative example 1
An NCM material for comparison was prepared, differing from example 1 only in that ammonium hydrogen phosphate and lanthanum hydroxide and boric acid were not added, and only lithium hydroxide and a positive electrode material precursor were added to be ball-milled.
Comparative example 2
A comparative LLP coated NCM material was prepared, differing from example 1 only in that no boric acid was added.
Example 2
Respectively weighing 0.003mol of ammonium dihydrogen phosphate, 0.0004mol of lanthanum oxide, 0.324mol of lithium hydroxide and 0.003mol of boron oxide into a 500mL ball milling tank filled with 200mL of propanol, adding 200g of zirconia grinding balls with the particle sizes of 8mm, 12mm and 15mm according to the mass ratio of 4:3:3, placing the ball milling tank on a ball mill, carrying out ball milling for 3h at the rotating speed of 500rmp, and then adding 0.3mol of Ni0.8Co0.1Mn0.1(OH)2The precursor is continuously ball-milled for 2h at the rotating speed of 100rmp, and the uniformly stirred mixture is taken out and then is dried for 24h at the temperature of 90 ℃ in a forced air drying oven. Placing the dried product in a mortar for grinding uniformly, sieving with a 400-mesh sieve, placing the powder in a tubular furnace for calcining at 450 ℃ for 6h, heating to 750 ℃ and calcining for 15h to obtain boron-doped product&LLP-coated LiNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Example 3
Respectively weighing 0.012mol of phosphoric acid, 0.0015mol of lanthanum oxide, 0.165mol of lithium hydroxide and 0.0015mol of boron oxide into a 1000mL ball milling tank filled with 200mL of propanol, adding 1000g of zirconia grinding balls with the grain diameters of 6mm, 10mm and 13mm according to the mass ratio of 3:3:3, placing the ball milling tank on a ball mill for ball milling for 30h at the rotating speed of 300rmp, and then adding 0.15mol of Ni0.825Co0.115Al0.06O2(OH)2The precursor is continuously ball-milled for 3h at the rotating speed of 300rmp, and the uniformly stirred mixture is taken out and then is dried for 24h in a forced air drying oven at the temperature of 100 ℃. Putting the dried product into a mortar for even grindingSieving with 500 mesh sieve, calcining the powder in a tube furnace at 450 deg.C for 6h, heating to 740 deg.C, calcining for 12h to obtain boron dope&LLP-coated LiNi0.825Co0.115Al0.06O2And (3) a positive electrode material.
Example 4
Respectively weighing 0.12mol of phosphoric acid, 0.03mol of lanthanum nitrate, 1.95mol of lithium hydroxide and 0.03mol of boron oxide into a 1000mL ball milling tank filled with 200mL of propanol, adding 3000g of zirconia grinding balls with the particle sizes of 8mm, 12mm and 16mm according to the mass ratio of 5:3:2, placing the ball milling tank on a ball mill for ball milling for 30h at the rotating speed of 400rmp, and then adding 1.5mol of Ni0.6Co02Mn0.2CO3And continuously performing ball milling on the precursor for 3h at the rotating speed of 400rmp, taking out the uniformly stirred mixture, and drying the mixture in a forced air drying oven at the temperature of 120 ℃ for 16 h. Placing the dried product in a mortar for grinding uniformly, sieving with a 500-mesh sieve, placing the powder in a tubular furnace for calcining at 480 ℃ for 8h, heating to 880 ℃ and calcining for 15h to obtain boron doped&(LLP) -coated LiNi0.6Co0.2Mn0.2O2And (3) a positive electrode material.
Example 5
Respectively weighing 0.12mol of phosphoric acid, 0.02mol of lanthanum oxide, 0.9mol of lithium carbonate and 0.02mol of boron oxide into a 1000mL ball milling tank filled with 300mL of propanol, adding 3000g of zirconia grinding balls with the particle sizes of 8mm, 12mm and 16mm according to the mass ratio of 5:3:2, placing the ball milling tank on a ball mill for ball milling for 2h at the rotating speed of 600rmp, and then adding 1.55mol of Ni0.75Cr0.1Mn0.15(OH)2And continuously performing ball milling on the precursor for 24h at the rotating speed of 750rmp, taking out the uniformly stirred mixture, and drying the mixture in a forced air drying oven at the temperature of 150 ℃ for 16 h. Placing the dried product in a mortar for grinding uniformly, sieving with a 750-mesh sieve, placing the powder in a tubular furnace for calcining at 550 ℃ for 8h, heating to 850 ℃ and calcining for 12h to obtain boron-doped product&LLP-coated LiNi0.75Cr0.1Mn0.15O2And (3) a positive electrode material.
Example 6
0.06mol of phosphoric acid and 0.01mol of lanthanum oxide were weighed out separatelyAdding 1.8mol of lithium nitrate and 0.08mol of boron oxide into a 1000mL ball-milling tank filled with 300mL of propanol, adding 1500g of zirconia grinding balls with the particle sizes of 8mm, 10mm and 12mm respectively according to the mass ratio of 3:5:4, placing the ball-milling tank on a ball mill for ball milling for 25h at the rotating speed of 100rmp, and then adding 1.5mol of Ni0.6Al0.25Co0.15(OH)2The precursor is continuously ball-milled for 25h at the rotating speed of 100rmp, and the uniformly stirred mixture is taken out and then is dried for 16h in a forced air drying oven at the temperature of 150 ℃. Placing the dried product in a mortar for grinding uniformly, sieving with a 100-mesh sieve, placing the powder in a tubular furnace for calcining at 350 ℃ for 8h, heating to 880 ℃ and calcining for 12h to obtain boron doped&LLP-coated LiNi0.6Al0.25Co0.15O2And (3) a positive electrode material.
Example 7
Respectively weighing 0.006mol of phosphoric acid, 0.002mol of lanthanum nitrate, 0.18mol of lithium hydroxide and 0.015mol of boric acid, adding the weighed materials into a 400mL ball-milling tank filled with 100mL of ethylene glycol, adding 3000g of zirconia grinding balls with the particle sizes of 8mm, 12mm and 14mm according to the mass ratio of 3:2:2, placing the ball-milling tank on a ball mill at the rotating speed of 500rmp for ball milling for 5 hours, and then adding 0.15mol of Ni0.95Mg0.025Al0.025(OH)2And continuously performing ball milling on the precursor for 20h at the rotating speed of 200rmp, taking out the uniformly stirred mixture, and drying the mixture in a forced air drying oven at the temperature of 150 ℃ for 16 h. Placing the dried product in a mortar for grinding uniformly, sieving with a 100-mesh sieve, placing the powder in a tubular furnace for calcining at 480 ℃ for 8h, heating to 720 ℃ and calcining for 10h to obtain boron dope&LLP-coated LiNi0.95Mg0.025Al0.025O2And (3) a positive electrode material.
Example 8
Respectively weighing 0.06mol of phosphoric acid, 0.02mol of lanthanum nitrate, 0.486mol of lithium hydroxide and 0.025mol of boron oxide into a 2000mL ball-milling tank filled with 100mL of ethylene glycol, adding 4000g of zirconia grinding balls with the particle sizes of 8mm, 12mm and 14mm according to the mass ratio of 3:2:2, placing the ball-milling tank on a ball mill for ball milling at the rotating speed of 500rmp for 5 hours, and then adding 0.3mol of Ni0.95Mg0.025Zr0.025(OH)2The precursor is continuously ball-milled for 20h at the rotating speed of 100rmp, and the uniformly stirred mixture is taken out and then is dried for 16h in a forced air drying oven at the temperature of 150 ℃. Placing the dried product in a mortar for grinding uniformly, sieving with a 250-mesh sieve, placing the powder in a tubular furnace for calcining at 480 ℃ for 8h, heating to 720 ℃ and calcining for 10h to obtain boron dope&LLP-coated LiNi0.95Mg0.025Zr0.025O2And (3) a positive electrode material.
Example 9
Respectively weighing 0.06mol of phosphoric acid, 0.015mol of lanthanum nitrate, 1.66mol of lithium nitrate and 0.025mol of boron oxide into a 2000mL ball milling tank filled with 400mL of ethylene glycol, adding 4000g of zirconia grinding balls with the particle sizes of 8mm, 12mm and 14mm according to the mass ratio of 3:2:2, placing the ball milling tank on a ball mill for ball milling for 4h at the rotating speed of 500rmp, and then adding 1.35mol of Ni0.95Mg0.025Cr0.025(OH)2The precursor is continuously ball-milled for 20h at the rotating speed of 100rmp, and the uniformly stirred mixture is taken out and then is dried for 16h in a forced air drying oven at the temperature of 150 ℃. Placing the dried product in a mortar for grinding uniformly, sieving with a 250-mesh sieve, placing the powder in a tubular furnace for calcining at 480 ℃ for 8h, heating to 720 ℃ and calcining for 12h to obtain boron dope&LLP-coated LiNi0.95Mg0.025Cr0.025O2And (3) a positive electrode material.
Phase detection
XRD examination of FIG. 1 demonstrates B prepared in example 1&LiLa (PO) corresponding to target substance LLP exists in LLP @ NCM material3)4The physical phase (marked with an asterisk) corresponds to the standard card number PDF # 35-0075.
The TEM inspection of FIG. 2 shows that the surface of the NCM cathode material is coated with a layer of material, wherein particle agglomeration occurs on the surface of the LLP coated sample (LLP @ NCM), which may be caused by uneven dispersion of the coating material. The co-modified sample (B & LLP @ NCM) after addition of the boron compound formed a more uniform coating on the surface compared to LLP @ NCM.
FIG. 3 shows B prepared in example 1&High resolution TEM image of LLP @ NCM material, from which it can be seen that the material is clearly presentIn the two phases, an I area is selected in the material for carrying out lattice spacing calibration, the lattice spacing is 0.2231nm, and the lattice spacing corresponds to a (101) crystal face of the NCM layered lithium-intercalation oxide cathode material; the calibration is carried out in a selected II area of the material close to the surface part, the lattice spacing is 0.4321nm, and the corresponding cladding LiLa (PO)3)4The (110) crystal plane of the monoclinic phase material.
In FIG. 4, the element distribution of the B & LLP @ NCM material prepared in example 1 is analyzed by SEM cross section and EDS mapping, which shows that the B element is uniformly dispersed into the interior of the material structure.
Performance testing
The charge and discharge tests were performed on button solid state batteries assembled from the materials of NCM, LLP @ NCM, and B & LLP @ NCM prepared in comparative example 1, comparative example 2, and example 1, and the results are shown in fig. 5.
Fig. 5a, cycle performance comparison.
Fig. 5b, rate performance comparison.
Claims (10)
1. A boron-doped and phosphite-coated nickel-based positive electrode material for a lithium ion all-solid battery is characterized in that: the material consists of a boron-doped lithium ion battery nickel-based positive electrode material and a phosphite coating layer on the surface of the material.
2. Boron doping for lithium ion all solid state batteries according to claim 1&The nickel-based anode material coated with the phosphite is characterized in that: the nickel-based anode material of the lithium ion battery is a layered lithium-intercalated oxide anode material, and the chemical composition of the nickel-based anode material is LiNixN1-xO2，0.6≤x<1, N is any one or more of Co, Mn, Al, Zr, Mg and Cr; the surface coating layer is polyanion phosphite LiLa1-yMy(PO3)4Y is more than or equal to 0 and less than or equal to 0.4, and M is any one or more of Co, Mn, Al, Cr, Zr, Mg and B.
3. The boron-doped & phosphite-coated nickel-based positive electrode material for the lithium-ion all-solid battery according to claim 1, wherein: the boron doping amount is 0.05-20% of the nickel-based anode material of the lithium ion battery, preferably 0.1-5%, and more preferably 0.5-3%, and the amount of the substance of the surface coating layer compound is 0.01-20%, preferably 0.1-10%, and more preferably 0.5-3% of the nickel-based anode material of the lithium ion battery.
4. The method for preparing a boron-doped and phosphite-coated nickel-based positive electrode material for a lithium ion all-solid battery according to any one of claims 1 to 3, wherein: respectively weighing a phosphorus source, a lanthanum source, a lithium source and a boron source according to a certain proportion, adding a dispersing agent into a ball milling tank for ball milling, then continuously ball milling the added precursor of the nickel-based positive electrode material of the lithium ion battery, taking out the uniformly stirred mixture and drying; and grinding the dried product uniformly, sieving, and calcining the powder to obtain the catalyst.
5. The method for preparing the boron-doped and phosphite-coated nickel-based positive electrode material for the lithium-ion all-solid battery according to claim 4, wherein the method comprises the following steps: the phosphorus source comprises: one or more of ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate and phosphoric acid, and the lanthanum source comprises: one or more of lanthanum hydroxide, lanthanum nitrate, lanthanum carbonate and lanthanum oxide; the lithium source includes: one or more of lithium hydroxide, lithium carbonate, lithium nitrate and lithium oxalate; the boron source includes: one or two of boric acid and boron oxide, and the dispersant comprises C, H, N, O element compound which is liquid at normal temperature, preferably ethylene glycol.
6. The method for preparing the boron-doped and phosphite-coated nickel-based positive electrode material for the lithium-ion all-solid battery according to claim 4, wherein the method comprises the following steps: phosphorus sources used in the raw materials: the molar ratio of P to La in the lanthanum source is 3-5: 1, boron source: the molar ratio of the precursor of the nickel-based positive electrode material of the lithium ion battery is 0.0005-0.3, and the molar ratio of the lithium source: the molar ratio of (0.25 multiplied by phosphorus source + lanthanum source + boron source + lithium ion battery nickel-based positive electrode material precursor) is 1-1.3, preferably 1.05-1.1.
7. The method for preparing the boron-doped and phosphite-coated nickel-based positive electrode material for the lithium-ion all-solid battery according to claim 4, wherein the method comprises the following steps: adding a phosphorus source, a lanthanum source, a lithium source and a boron source, and performing ball milling after a dispersing agent at a rotation speed of 50-800rpm, preferably 200-500 rpm; the volume ratio of the raw materials to the grinding balls is 0.1-10, preferably 0.3-3; the grinding time is controlled to be 2-48h, preferably 3-10 h; adding the nickel-based positive electrode material precursor of the lithium ion battery, and continuing to perform ball milling for 2-24h, preferably 3-8h at the rotating speed of 50-800rmp, preferably 100-300 rpm.
8. The method for preparing the boron-doped and phosphite-coated nickel-based positive electrode material for the lithium-ion all-solid battery according to claim 4, wherein the method comprises the following steps: the calcination is divided into two stages, the first stage calcination temperature is 300-600 ℃, preferably 450-550 ℃, the time is 2-10h, preferably 4-8h, and the second stage calcination temperature is 600-900 ℃, preferably 650-800 ℃, the time is 7-36h, preferably 8-15 h.
9. The use of the boron-doped and phosphite-coated nickel-based positive electrode material for lithium ion all-solid-state batteries according to any one of claims 1 to 3, or the boron-doped and phosphite-coated nickel-based positive electrode material for lithium ion all-solid-state batteries prepared by the preparation method according to any one of claims 4 to 8, for preparing a positive electrode material for all-solid-state lithium ion batteries; especially the application in the positive electrode material for sulfur-based solid electrolyte all-solid-state lithium ion battery.
10. The use of claim 9, wherein the lithium-ion all-solid-state battery is doped with boron&The solid electrolyte used in the solid lithium ion battery with the phosphite coated nickel-based positive electrode material comprises Li9.54Si1.74P1.44S11.7Cl0.3、Li7P3S11、Li10GeP2S12Any one of the above.
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