CN115764013A - Positive electrode lithium supplement material, preparation method and application thereof - Google Patents
Positive electrode lithium supplement material, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a positive electrode lithium supplement material, a preparation method and application thereof; the positive electrode lithium supplement material comprises a positive electrode lithium supplement agent and solid electrolyte coated on the surface of the positive electrode lithium supplement; wherein the positive electrode lithium supplement agent is selected from Li 2 O、Li 2 NiO 2 、Li 2 S、Li 2 S 2 One or more of the above; the solid electrolyte is selected from Li 3 InCl 6 、Li 6 PS 5 Cl、Li 7 P 3 S 11 、Li 10 GeP 2 S 12 、Li 4‑x Sn 1‑x M x S 4 One or more of them. According to the invention, the solid electrolyte is coated on the surface of the positive electrode lithium supplement agent to prepare the positive electrode lithium supplement material, so that the problem of poor contact stability of the positive electrode lithium supplement agent and the electrolyte under high potential is solved; the positive electrode lithium supplement material is added into the positive electrode active material to prepare the positive electrode material, so that the first discharge gram capacity and the cycle stability of the positive electrode material can be improved.
Description
Technical Field
The invention belongs to the technical field of new electrochemical materials, and particularly relates to a positive electrode lithium supplement material, a preparation method and application thereof.
Background
A lithium ion battery may form an SEI film on a negative electrode during a first charge and discharge process, which may consume a large amount of active lithium, resulting in a decrease in initial capacity and a decrease in cycle life of the battery. At present, the main solution is to supplement the loss of active lithium by a lithium supplement technology. The lithium supplement technology is mainly divided into positive electrode lithium supplement and negative electrode lithium supplement. The lithium supplement of the negative electrode mainly comprises the step of directly contacting the negative electrode with lithium metal to play a role in pre-lithiation, but the introduction of the metal lithium greatly increases the safety problem and the difficulty of the preparation process. The positive pole lithium supplement is characterized in that a positive pole lithium supplement agent is added in the battery homogenizing process, so that the loss of active lithium in the first charging process can be effectively improved. The positive electrode lithium supplement agent generally has the characteristics of high capacity and low first effect, and a large amount of Li is removed in the charging process + Used for forming SEI film, does not accept large amount of Li during discharge + Thereby increasing the capacity of the battery.
In the prior art, the lithium-supplemented positive electrode usually comprises a binary lithium-containing compound (such as Li) 2 O、Li 2 O 2 、Li 3 N, etc.), ternary lithium-containing compound (Li) 4 FeO 5 、Li 6 CoO 4 、Li 2 NiO 2 Etc.) and the like. The binary lithium-containing compound has low decomposition potential but poor stability and is easy to generate gas, and the influence on the performance of the battery brings potential safety hazards; the ternary lithium-containing compound has high irreversible capacity and good environmental stability, but the decomposition product increases the quality of the electrode and the decomposition voltage is higher and incompatible with most anode materials.
The invention patent CN 114597525A discloses a lithium ion battery and its application, the lithium ion battery includes a lithium supplement agent Li 2 NiO 2 The cut-off voltage of the formed lithium ion battery is 4.0V to 4.5V, and the lithium supplement agent generates more oxygen in the formation stage by adopting higher voltage in the formation stage, so that the gas generation in the storage stage is reduced, and the stability and the safety of the battery are improved. However, due to the use of Li as a lithium-supplementing agent 2 NiO 2 Sensitive to moisture, so that the manufacturing process of the battery has higher requirements, and in addition, the lithium supplement agent Li 2 NiO 2 So that Li is poor in conductivity + The stripping efficiency is low, which leads to the increase of battery polarization and further influences the safety performance of the battery.
The invention patent CN 107863567A discloses a lithium supplement additive for a lithium ion battery anode and application thereof, and conductive metal doped Li is used 2 The O powder is used for preparing the anode lithium supplement material, so that the lithium supplement effect is achieved, and a foundation is laid for preparing a high-capacity lithium ion battery. However, due to Li 2 O powder is easy to absorb water to generate strong base LiOH, so that PVDF (polyvinylidene fluoride) as a binder is easy to decompose and inactivate, and the positive slurry is condensed and cannot be coated; in addition, li 2 The conductivity of O is poor, the O cannot be completely decomposed in the first charging process, and gas can still be generated in the subsequent charging and discharging processes, so that the safety performance of the battery is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a positive electrode lithium supplement material, a preparation method and application thereof. According to the invention, the solid electrolyte is coated on the surface of the positive electrode lithium supplement agent to prepare the positive electrode lithium supplement material with the core-shell structure, and the problem of poor contact stability of the positive electrode lithium supplement agent and the electrolyte under high potential is solved by coating the solid electrolyte; second, the ionic conductivity of the solid electrolyte: (>10 -3 S/cm) is far larger than the positive active material and the positive lithium supplement agent, so that the conductivity of the material can be improved, and the stability of the material in the air can be improved to a certain extent; adding the positive electrode lithium-supplementing material into the positive electrode active material to obtain the positive electrode materialThe first discharge capacity and the cycle stability of the anode material are improved.
In order to achieve the above object, a first aspect of the present invention provides a positive electrode lithium supplement material, which adopts the following technical scheme:
a positive electrode lithium supplement material comprises a positive electrode lithium supplement agent and a solid electrolyte coated on the surface of the positive electrode lithium supplement agent; wherein the positive electrode lithium supplement agent is selected from Li 2 O、Li 2 NiO 2 、Li 2 S、Li 2 S 2 One or more of the above;
the solid electrolyte is selected from Li 3 InCl 6 、Li 6 PS 5 Cl、Li 7 P 3 S 11 、Li 10 GeP 2 S 12 、Li 4-x Sn 1-x M x S 4 One or more of them.
In the above-described positive electrode lithium-supplementing material, as a preferred embodiment, the solid electrolyte is selected from Li 3 InCl 6 、Li 4-x Sn 1-x M x S 4 Wherein the Li 4-x Sn 1-x M x S 4 Wherein M is selected from at least one of As, sb and Bi, 0 < x < 0.5 (e.g., x =0.01, x =0.05, x =0.08, x =0.1, x =0.2, x =0.3, x = 0.4).
In the present invention, the above Li is selected 3 InCl 6 、Li 6 PS 5 Cl、Li 7 P 3 S 11 、Li 10 GeP 2 S 12 、Li 4-x Sn 1-x M x S 4 The reason that one or more of the solid electrolytes (M is a doping element) is that the solid electrolytes have high ionic conductivity, and the solid electrolytes are coated on the surface of the positive electrode lithium supplement agent to form the positive electrode lithium supplement material with the core-shell structure, so that the problem that the positive electrode lithium supplement agent is poor in contact stability with electrolyte under high potential is solved, particularly the problem that the Li is poor in contact stability with the electrolyte under high potential 3 InCl 6 And Li 4-x Sn 1-x M x S 4 The solid electrolyte has good air stability, and can avoid direct contact between the air-unstable positive electrode lithium supplement agent and air;further, the ion conductivity of the above solid electrolyte: (>10 -3 S/cm) is far larger than the positive active material and the positive lithium supplement agent, so that the conductivity of the material can be improved, and the lithium supplement effect of the material can be improved.
In the above-mentioned lithium replenishing material for a positive electrode, as a preferred embodiment, the mass ratio of the solid electrolyte to the lithium replenishing agent for a positive electrode is (1-5): (95-99) (such as 2.
The mass ratio of the solid electrolyte to the positive electrode lithium supplement agent is limited to (1-5): (95-99), the conductivity of the positive electrode lithium supplement material can be improved in the range, and the positive electrode lithium supplement material is favorable for achieving a better lithium supplement effect; if the mass of the solid electrolyte is excessively added, the first discharge gram capacity of the anode material prepared by adding the anode lithium supplement material into the anode active material is lower; if the mass of the solid electrolyte is added too little, the coating effect of the positive electrode lithium supplement material is poor, the lithium supplement effect is not obvious, and the cycling stability of the positive electrode material prepared by adding the solid electrolyte into the positive electrode active material is poor.
The second aspect of the present invention provides a preparation method of the above positive electrode lithium supplement material, including:
s1, performing ball milling treatment on a positive electrode lithium supplement agent and a solid electrolyte to obtain a mixture;
and S2, sintering the mixture to obtain the anode lithium supplement material.
In the above manufacturing method, as a preferred embodiment, in the step S1, the positive electrode lithium supplement agent is selected from Li 2 O、Li 2 NiO 2 、Li 2 S、Li 2 S 2 One or more of the above; preferably, the solid electrolyte is selected from Li 3 InCl 6 、Li 6 PS 5 Cl、Li 7 P 3 S 11 、Li 10 GeP 2 S 12 、Li 4-x Sn 1-x M x S 4 One or more of the above; preferably, the mass ratio of the solid electrolyte to the positive electrode lithium supplement agent is (1-5): (95-99) (such as 2.
In the above preparation method, as a preferred embodiment, in the step S1, the ball milling process is performed in a ball mill, the ball milling rotation speed is 300-500rpm (such as 350rpm, 400rpm, 450 rpm), and the ball milling time is 5-15h (such as 8h, 10h, 12 h).
In the above-mentioned preparation method, as a preferred embodiment, in the step S2, the sintering treatment is performed under an inert atmosphere, the sintering temperature is 400 to 700 ℃ (such as 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃) and the sintering time is 6 to 10 hours (such as 7 hours, 8 hours, 9 hours).
The sintering temperature is limited to 400-700 ℃, and the solid electrolyte can be better coated on the surface of the positive lithium supplement agent in the temperature range; if the sintering temperature is too low, the coating effect is poor; if the sintering temperature is too high, part of the materials will volatilize, and the coating effect is not good.
The third aspect of the invention provides a positive electrode material, which comprises a positive electrode active material and the positive electrode lithium supplement material or the positive electrode lithium supplement material prepared by the preparation method; the positive active material is lithium iron phosphate, lithium manganese iron phosphate, lithium cobaltate, lithium nickel cobalt aluminate, lithium nickel cobalt manganese oxide and a lithium-rich manganese-based positive material.
In the above-described positive electrode material, as a preferred embodiment, the positive electrode lithium-supplementing material accounts for 0.5% to 10% (e.g., 1%, 2%, 3%, 5%, 7%, 9%) of the mass of the positive electrode active material.
The method comprises the following steps that a certain amount of positive active lithium is irreversibly consumed on the surface of a negative electrode of the battery in the process of forming an SEI film, so that the problems of low first-cycle coulombic efficiency, poor cycle life and the like of the battery are caused; if the added mass of the positive electrode lithium supplement material is too small, the energy density and the cycle performance of the battery are not obviously improved, and if the added mass of the positive electrode lithium supplement material is too large, the capacity of the battery is attenuated.
The invention also provides a preparation method of the cathode material.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the solid electrolyte is coated on the surface of the positive electrode lithium supplement agent to prepare the positive electrode lithium supplement material with the core-shell structure, so that the problem of poor contact stability of the positive electrode lithium supplement agent and the electrolyte under high potential is solved.
(2) The invention utilizes the ionic conductivity of solid electrolyte (>10 -3 S/cm) is far larger than the positive active material and the positive lithium supplement agent, so that the conductivity of the material can be improved, and the stability of the material in the air can be improved to a certain extent; the positive electrode lithium supplement material is added into the positive electrode active material to prepare the positive electrode material, so that the first discharge gram capacity and the cycle stability of the positive electrode material can be improved.
(3) The preparation method of the anode lithium supplement material is simple, low in cost and easy for industrial production.
Drawings
Fig. 1 is a charge-discharge curve at a rate of 0.1C after a button cell is assembled from a positive electrode material obtained by mixing a positive electrode lithium supplement material prepared in example 1 of the present invention and a positive electrode active material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The examples of the present invention are carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and process parameters of the following examples, which do not indicate specific conditions, are generally in accordance with conventional conditions.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, all numerical values relating to amounts of components are "parts by weight" throughout, unless otherwise specified and/or indicated. The process parameters for the following examples, without specifying the particular conditions, are generally in accordance with conventional conditions. The starting materials described in the following examples are all commercially available from the public. Li used in examples of the present invention 3 InCl 6 The preparation method of the solid electrolyte comprises the following steps: liCl and InCl were weighed according to a molar ratio of 3 3 Uniformly mixing to obtain a mixture, and then adding deionized water with the mass 2 times that of the mixture to disperse to obtain a precursor solution; then heating for 4-8h at 180-300 ℃ under the vacuum or inert gas condition to obtain Li 3 InCl 6 A solid electrolyte.
Li used 4-x Sn 1-x M x S 4 The preparation method comprises the following steps: snS is weighed according to the molar ratio of (1-x) 0.5x (2-0.5 x) (x is more than 0 and less than 0.5) 2 、M 2 S 5 (M is at least one selected from As, sb and Bi) and Na 2 S, putting the mixture into deionized water in air, grinding the mixture uniformly, and then removing a solvent through vacuum drying to obtain mixed powder; then sintering the mixed powder at 400-600 ℃ for 8-15h under inert atmosphere to obtain Na 4-x Sn 1-x M x S 4 Solid electrolyte powder; then Na is added 4-x Sn 1- x M x S 4 Solid electrolyte powder is put into a nonpolar extractant of lithium ethoxide, and extracted Li is obtained through multi-stage solid phase extraction 4-x Sn 1-x M x S 4 A solid electrolyte precursor; finally, li is added 4-x Sn 1-x M x S 4 After the solid electrolyte precursor is fully dried, the solid electrolyte precursor is placed in argonSintering at 450-550 deg.C for 5-10h in atmosphere to obtain Li 4-x Sn 1-x M x S 4 A solid electrolyte.
Li used 7 P 3 S 11 The preparation method comprises the following steps: weighing Li according to a molar ratio of 7 2 S、P 2 S 5 Placing the mixture into anhydrous acetonitrile to be uniformly mixed, wherein the mass of the anhydrous acetonitrile is Li 2 S、P 2 S 5 Stirring the solid phase powder for 12 to 24 hours at 600 to 800rpm at 50 to 80 ℃ for 8 to 20 times of the mass of the solid phase powder to obtain a mixed solution, heating the mixed solution at 80 to 100 ℃ for 10 to 12 hours to evaporate acetonitrile to obtain white powder, heating the white powder to 200 to 300 ℃ at a heating rate of 3 to 5 ℃/min in a muffle furnace, and keeping the temperature for 0.5 to 2 hours to obtain the solid electrolyte Li 7 P 3 S 11 . The specific embodiment of the invention provides a preparation method of a positive electrode lithium supplement material, which comprises the following steps:
s1, performing ball milling treatment on a positive electrode lithium supplement agent and a solid electrolyte in a ball mill at the ball milling rotation speed of 300-500rpm for 5-15h to obtain a mixture, wherein the positive electrode lithium supplement agent is selected from Li 2 O、Li 2 NiO 2 、Li 2 S、Li 2 S 2 The mass ratio of the solid electrolyte to the positive electrode lithium supplement agent is (1-5): (95-99);
s2, sintering the mixture at the temperature of 400-700 ℃ for 6-10h in an inert atmosphere to obtain a positive electrode lithium supplement material;
wherein the solid electrolyte is selected from Li 3 InCl 6 、Li 6 PS 5 Cl、Li 7 P 3 S 11 、Li 10 GeP 2 S 12 、Li 1-x Sn 1-x M x S 4 One or more of them.
The present invention will be described in further detail with reference to specific examples.
Among them, li in examples 1 to 3 and comparative examples 3 to 4 3 InCl 6 The preparation method of the solid electrolyte comprises the following steps: liCl and InCl were weighed according to a molar ratio of 3 3 Uniformly mixing to obtain a mixture, and then adding deionized water with the mass 2 times that of the mixture to disperse to obtain a precursor solution; then heating for 6h at 250 ℃ under the condition of nitrogen to obtain Li 3 InCl 6 A solid electrolyte.
Li in examples 4 to 6 4-x Sn 1-x As x S 4 The preparation method of the solid electrolyte comprises the following steps: snS is weighed according to the molar ratio of (1-x) to 0.5x (2-0.5 x) 2 、As 2 S 5 And Na 2 S, putting the mixture into deionized water in air, grinding the mixture uniformly, and then removing a solvent through vacuum drying to obtain mixed powder; then sintering the mixed powder at 500 ℃ for 12 hours in nitrogen atmosphere to obtain Na 4-x Sn 1-x As x S 4 Solid electrolyte powder; then Na is added 4-x Sn 1-x As x S 4 Putting the solid electrolyte powder into a nonpolar extractant of lithium ethoxide, and performing multi-stage solid-phase extraction to obtain extracted Li 4-x Sn 1-x M x S 4 A solid electrolyte precursor; finally, li is added 4-x Sn 1-x As x S 4 After the solid electrolyte precursor is fully dried, the solid electrolyte precursor is placed in an argon atmosphere to be sintered for 8 hours at the temperature of 500 ℃ to obtain Li 4-x Sn 1-x As x S 4 A solid electrolyte; wherein SnS is shown in examples 4 to 6 2 、As 2 S 5 And Na 2 The molar ratio of S is respectively as follows: 0.8.
Li in example 7 3.8 Sn 0.8 Sb 0.2 S 4 The preparation method of the solid electrolyte comprises the following steps: the SnS is weighed according to the molar ratio of 0.8 2 、Sb 2 S 5 And Na 2 S, putting the mixture into deionized water in air, grinding the mixture uniformly, and then removing a solvent through vacuum drying to obtain mixed powder; then sintering the mixed powder at 500 ℃ for 12h in nitrogen atmosphere to obtain Na 3.8 Sn 0.8 Sb 0.2 S 4 Solid electrolyte powder; then Na is added 3.8 Sn 0.8 Sb 0.2 S 4 Solid state electrolysisPlacing the mass powder in a nonpolar extractant of lithium ethoxide, and performing multi-stage solid-phase extraction to obtain an extracted solid electrolyte precursor; finally, after fully drying the solid electrolyte precursor, placing the solid electrolyte precursor in an argon atmosphere to carry out sintering at the temperature of 500 ℃ for 8 hours to obtain Li 3.8 Sn 0.8 Sb 0.2 S 4 A solid electrolyte.
Li in example 8 7 P 3 S 11 The preparation method of the solid electrolyte comprises the following steps: weighing Li according to a molar ratio of 7 2 S、P 2 S 5 Placing the mixture into anhydrous acetonitrile to be uniformly mixed, wherein the adding mass of the anhydrous acetonitrile is Li 2 S and P 2 S 5 10 times of the mass of the solid electrolyte Li, stirring the mixture for 24 hours at 600rpm at 50 ℃ to obtain a mixed solution, heating the mixed solution at 80 ℃ for 12 hours to evaporate acetonitrile to obtain white powder, heating the white powder to 260 ℃ in a muffle furnace at a heating rate of 3 ℃/min, and keeping the temperature for 1 hour to obtain the solid electrolyte Li 7 P 3 S 11 。
Embodiment 1 a method for preparing a positive electrode lithium supplement material, comprising:
s1, mixing Li 2 NiO 2 And Li 3 InCl 6 Adding the mixture into a ball mill according to the mass ratio of 98;
and S2, calcining the mixture at 500 ℃ for 8h in a nitrogen atmosphere to obtain the anode lithium supplement material.
Embodiment 2 is a method for preparing a positive electrode lithium supplement material, including:
s1, mixing Li 2 NiO 2 And Li 3 InCl 6 Adding the mixture into a ball mill according to the mass ratio of 99;
and S2, calcining the mixture at 500 ℃ for 8h in a nitrogen atmosphere to obtain the anode lithium supplement material.
Embodiment 3 is a method for preparing a positive electrode lithium supplement material, including:
s1, mixing Li 2 NiO 2 And Li 3 InCl 6 Adding the mixture into a ball mill according to a mass ratio of 95Ball milling is carried out for 8 hours at a ball milling speed of 00rpm to obtain a mixture;
and S2, calcining the mixture at 500 ℃ for 8h in a nitrogen atmosphere to obtain the anode lithium supplement material.
Embodiment 4 is a method for preparing a positive electrode lithium supplement material, including:
s1, mixing Li 2 S and Li 3.8 Sn 0.8 As 0.2 S 4 Adding the mixture into a ball mill according to the mass ratio of 95;
and S2, calcining the mixture for 8 hours at 500 ℃ in a nitrogen atmosphere to obtain the anode lithium supplement material.
Example 5
Example 5 differs from example 4 in that Li is added 3.8 Sn 0.8 As 0.2 S 4 Substitution with Li 3.9 Sn 0.9 As 0.1 S 4 Otherwise, the same procedure as in example 4 was repeated.
Example 6
Example 6 differs from example 4 in that Li is added 3.8 Sn 0.8 As 0.2 S 4 Substitution with Li 3.6 Sn 0.6 As 0.4 S 4 Otherwise, the same procedure as in example 4 was repeated.
Example 7
Example 7 differs from example 4 in that Li is added 3.8 Sn 0.8 As 0.2 S 4 Replacement by Li 3.8 Sn 0.8 Sb 0.2 S 4 Otherwise, the same procedure as in example 4 was repeated.
Embodiment 8 a method for preparing a positive electrode lithium supplement material, comprising:
s1, adding Li 2 NiO 2 And Li 7 P 3 S 11 Adding the mixture into a ball mill according to the mass ratio of 98;
and S2, calcining the mixture at 500 ℃ for 8h in a nitrogen atmosphere to obtain the anode lithium supplement material.
Comparative example 1
In comparative example 1, the positive electrode lithium-supplementing material was Li 2 NiO 2 。
Comparative example 2
In comparative example 2, the positive electrode lithium-supplementing material was Li 2 S。
Comparative example 3
Comparative example 3 differs from example 1 in that Li 2 NiO 2 And Li 3 InCl 6 The mass ratio of (2 a) to (b) was 99.5, and the rest was the same as in example 1.
Comparative example 4
Comparative example 4 differs from example 1 in that Li 2 NiO 2 And Li 3 InCl 6 The mass ratio of (3) to (7) was 93.
Performance testing
The positive electrode lithium-supplement materials of examples 1 to 8 and comparative examples 1 to 4 were mixed with a positive electrode active material LiFePO 4 Mixing the materials according to a mass ratio of 3: 0.5:0.7:2, mixing the mixture with Surpe-P, CNT and PVDF in a mass ratio, preparing slurry by using NMP as a solvent, coating the slurry on a metal aluminum foil to prepare a positive electrode, and finally cutting the positive electrode into a circular pole piece with the diameter of 12mm by using a punch as a working electrode; in a clean glove box (O) filled with Ar 2 The content is less than 0.1ppm 2 O content less than 0.1 ppm), a lithium sheet is taken as a negative electrode, a diaphragm is a polypropylene microporous membrane, and electrolyte is 1mol/L lithium hexafluorophosphate (LiPF) 6 ) (EC: DEC = 1), preparing a CR2032 type button cell according to a certain assembly process, and standing for 24 hours after the assembly process is finished so as to fully infiltrate the electrolyte and the electrode material. The 0.1C multiplying power charge-discharge test and the cycle performance test are carried out under the voltage range of 2.0-3.65V at the room temperature (25 ℃ plus or minus 1).
TABLE 1
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A positive electrode lithium supplement material, comprising: the lithium ion battery comprises a positive electrode lithium supplement agent and a solid electrolyte coated on the surface of the positive electrode lithium supplement agent;
wherein the positive electrode lithium supplement agent is selected from Li 2 O、Li 2 NiO 2 、Li 2 S、Li 2 S 2 One or more of the above; the solid electrolyte is selected from Li 3 InCl 6 、Li 6 PS 5 Cl、Li 7 P 3 S 11 、Li 10 GeP 2 S 12 、Li 4-x Sn 1-x M x S 4 One or more of them.
2. The positive lithium supplement material of claim 1, wherein the solid electrolyte is selected from Li 3 InCl 6 、Li 4-x Sn 1-x M x S 4 Wherein, the Li 4-x Sn 1-x M x S 4 Wherein M is at least one of As, sb and Bi, and x is more than 0 and less than 0.5.
3. The positive lithium supplement material according to claim 1 or 2, wherein the mass ratio of the solid electrolyte to the positive lithium supplement agent is (1-5): (95-99).
4. A method for producing a positive electrode lithium supplement material according to any one of claims 1 to 3, comprising:
s1, performing ball milling treatment on a positive electrode lithium supplement agent and a solid electrolyte to obtain a mixture;
and S2, sintering the mixture to obtain the anode lithium supplement material.
5. The method according to claim 4, wherein in the step S1, the positive electrode lithium supplement agent is selected from Li 2 O、Li 2 NiO 2 、Li 2 S、Li 2 S 2 One or more of the above; the solid electrolyte is selected from Li 3 InCl 6 、Li 6 PS 5 Cl、Li 7 P 3 S 11 、Li 10 GeP 2 S 12 、Li 4-x Sn 1-x M x S 4 One or more of the above; the mass ratio of the solid electrolyte to the positive electrode lithium supplement agent is (1-5): (95-99).
6. The preparation method according to claim 4 or 5, wherein in the step S1, the ball milling treatment is carried out in a ball mill, the ball milling rotation speed is 300-500rpm, and the ball milling time is 5-15h.
7. The method according to any one of claims 4 to 6, wherein in the step S2, the sintering treatment is performed under an inert atmosphere, the sintering temperature is 400 to 700 ℃, and the sintering time is 6 to 10 hours.
8. A positive electrode material, comprising: a positive electrode active material and the positive electrode lithium supplement material according to any one of claims 1 to 3 or the positive electrode lithium supplement material prepared by the preparation method according to any one of claims 4 to 7; the positive active material is selected from one or more of lithium iron phosphate, lithium manganese iron phosphate, lithium cobaltate, lithium nickel cobalt aluminate, lithium nickel cobalt manganate and a lithium-rich manganese-based positive material.
9. The positive electrode material according to claim 8, wherein the positive electrode lithium supplement material accounts for 0.5-10% by mass of the positive electrode active material.
10. Use of a positive electrode material according to claim 8 or claim 9 in a lithium ion battery.
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| CN117559013A (en) * | 2023-11-22 | 2024-02-13 | 高能时代(珠海)新能源科技有限公司 | Lithium supplementing agent composite material and preparation method and application thereof |
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