CN114497514B - Positive electrode lithium supplementing agent and application thereof - Google Patents
Positive electrode lithium supplementing agent and application thereof Download PDFInfo
- Publication number
- CN114497514B CN114497514B CN202210254003.2A CN202210254003A CN114497514B CN 114497514 B CN114497514 B CN 114497514B CN 202210254003 A CN202210254003 A CN 202210254003A CN 114497514 B CN114497514 B CN 114497514B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- lithium
- feo
- agent
- nio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode lithium supplementing agent and application thereof, wherein the positive electrode lithium supplementing agent is of a core-shell structure, and a core body comprises Li 5 FeO 4 The shell comprises Li 2 NiO 2 . The invention adopts Li as the lithium supplementing agent 2 NiO 2 Coating Li 5 FeO 4 Avoid Li 5 FeO 4 Contact with air, promote Li 5 FeO 4 To make Li 5 FeO 4 Can exert the capacity to the maximum extent, and Li 2 NiO 2 The lithium ion battery also has a lithium supplementing effect, and the energy density and the cycling stability of the battery can be improved by utilizing the lithium supplementing effect of the lithium ion battery and the lithium ion battery.
Description
Technical Field
The invention belongs to the field of batteries, and relates to a lithium supplementing agent, in particular to a positive electrode lithium supplementing agent and application thereof.
Background
In a lithium ion battery, the side with lower positive and negative pole initial coulombic efficiency determines the initial efficiency of the whole battery, and when the positive and negative pole efficiency is the same, the utilization rate of active lithium in the battery is the highest. The primary efficiency of the current commercial system is limited by the lower primary efficiency of the negative electrode. Therefore, much of the active Li provided by the positive electrode is consumed, and the energy density of the battery as a whole is lowered.
Lithium ion supplementing material Li widely studied at present 5 FeO 4 (LFO) can release four equivalent lithium ions, has high theoretical capacity (726 mAh/g), and has extremely poor reversibility (coulombic efficiency<10 percent) is an ideal lithium supplementing additive. However, LFO is unstable in air and absorbs moisture easily to form inactive Li x Fe y O z Residual alkali (Li) 2 CO 3 LiOH), which not only reduces the electrochemical activity of the battery, but also causes the battery to produce gas due to the existence of residual alkali, thereby causing potential safety hazard.
Based on the above research, it is necessary to provide a positive electrode lithium-supplementing agent which has good stability and high theoretical capacity, and can improve the energy density and the cycle stability of the battery.
Disclosure of Invention
The invention aims to provide a positive electrode lithium supplementing agent and application thereof, wherein the positive electrode lithium supplementing agent is of a core-shell structure, a core body is LFO, and a shell with a lithium supplementing effect wraps the LFO, so that the oxidization of the LFO in the air is inhibited, the energy density and the cycle stability of a battery are improved, and the safety problem caused by independent addition of the LFO is avoided.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode lithium-supplementing agent, which has a core-shell structure, wherein the core comprises Li 5 FeO 4 The shell comprises Li 2 NiO 2 。
The invention adopts Li as the lithium supplementing agent 2 NiO 2 (LNO) coating Li 5 FeO 4 The LNO can avoid Li 5 FeO 4 Contact with air, promote Li 5 FeO 4 To make Li 5 FeO 4 Can exert the capacity to the maximum extent, and Li 2 NiO 2 Also has tonic effectThe lithium effect can be utilized to improve the energy density and the cycling stability of the battery.
Preferably, the housing further comprises carbon.
The shell of the invention also comprises conductive carbon, and two coating materials can further coat Li 5 FeO 4 In the process of lifting Li 5 FeO 4 The stability of the lithium ion battery is improved, and the conductivity of the positive electrode lithium supplementing agent is also improved.
Preferably, the Li 5 FeO 4 And Li (lithium) 2 NiO 2 The mass ratio of (1 to 10): (1 to 10), which may be, for example, 1:1, 5:1, 10:1, 1:5 or 1:10, but is not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the Li 5 FeO 4 The mass ratio to carbon is (1 to 20): 1, and may be, for example, 1:1, 5:1, 10:1, 15:1, or 20:1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The nuclear Li of the invention 5 FeO 4 The mass ratio of LiFePO to the shell is in a reasonable range 4 If too much, the coating of the shell will be uneven, affecting Li 5 FeO 4 Capacity exertion, li 5 FeO 4 When the amount is too small, the optimal lithium supplementing effect is not achieved.
Preferably, the Li 5 FeO 4 Particle diameter D of (2) 50 For example, 5 μm to 12 μm, may be 5 μm, 8 μm, 10 μm, or 12 μm, but are not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Li according to the invention 5 FeO 4 Particle diameter D of (2) 50 The larger the particle size, the better the stability, but the particle size D 50 Too large will result in uneven LNO coverage; particle size D of LFO 50 The smaller the specific surface area, the larger the area exposed to air, and the faster the deterioration of the lithium-compensating agent.
The preparation method of the positive electrode lithium supplementing agent comprises the following steps of Li 5 FeO 4 Precursor and Li 2 NiO 2 Precursor, or Li 5 FeO 4 With Li 2 NiO 2 Coating the precursor of the two;
the coating mode comprises blending or co-sintering.
Preferably, the precursor comprises any one or a combination of at least two of a hydroxide, an oxide, an acetate or a carbonate of the corresponding metal, typically but not limited to a combination comprising a hydroxide and an oxide, a combination of an acetate and a carbonate, or a combination of a hydroxide and an acetate.
Preferably, the blending comprises dry blending or wet blending.
Preferably, the temperature of the co-sintering is 450 ℃ to 900 ℃, for example, 450 ℃, 500 ℃,600 ℃, 700 ℃, 800 ℃ or 900 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the co-sintering time is 2h to 40h, for example, 2h, 10h, 20h, 30h or 40h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the atmosphere of the co-sintering is argon and/or nitrogen.
As a preferred preparation method of the positive electrode lithium supplementing agent of the present invention, li is included 5 FeO 4 With Li 2 NiO 2 And (3) performing co-sintering on the precursors of the two to obtain the positive electrode lithium supplementing agent.
In a second aspect, the present invention provides a positive electrode sheet including a positive electrode active material, a conductive agent, a binder, and a positive electrode lithium supplementing agent;
the positive electrode lithium-supplementing agent is the positive electrode lithium-supplementing agent according to the first aspect.
Preferably, the mass ratio of the positive electrode lithium supplementing agent, the positive electrode active material, the conductive agent and the binder is (0.1 to 10): (90 to 99): (1 to 2): 1, for example, may be 5:95:1.5:1, 0.1:90:2:1, 10:99:2:1 or 0.1:99:1.5:1, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the positive electrode active material includes LiNi x Co y Mn 1-x-y O 2 And/or LiFePO 4 (lithium iron phosphate), wherein 0.5.ltoreq.x.ltoreq.0.9, may be, for example, 0.5, 0.7 or 0.9, 0.ltoreq.y.ltoreq.0.2, may be, for example, 0, 0.1 or 0.2, but are not limited to the values recited, other values not recited in the numerical range being equally applicable.
Preferably, the LiNi x Co y Mn 1-x-y O 2 In the form of a secondary sphere or a single crystal.
Preferably, the LiNi in the form of a secondary sphere x Co y Mn 1-x-y O 2 Particle diameter D of (2) 50 For example, 9 μm to 25 μm, may be 9 μm, 10 μm, 15 μm, 20 μm or 25 μm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the LiNi in single crystal form x Co y Mn 1-x-y O 2 Particle diameter D of (2) 50 For example, 1.5 μm to 6 μm, may be 1.5 μm, 2 μm, 3 μm, 4 μm, 5 μm or 6 μm, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the LiFePO 4 Comprises spherical lithium iron phosphate and/or nano lithium iron phosphate.
Preferably, the particle diameter D of the spherical lithium iron phosphate 50 For example, 5 μm to 15 μm, may be 5 μm, 8 μm, 10 μm, 13 μm or 15 μm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the particle diameter D of the nano lithium iron phosphate 50 For example, 0.3 μm to 2.4 μm, 0.3 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm or 2.4 μm may be used, but the values are not limited to those recited, and other values not recited in the numerical range are equally applicable.
In a third aspect, the present invention provides an electrochemical device comprising the positive electrode sheet according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
the invention is characterized in that the lithium supplementing agent Li 5 FeO 4 Is coated with Li 2 NiO 2 Avoid Li 5 FeO 4 The deterioration of the material due to contact with air affects the capacity of the material, and Li 2 NiO 2 Has better stability in the environment and is also a lithium supplementing agent, thereby inhibiting Li 5 FeO 4 And the energy density and the cycling stability density of the battery can be improved by utilizing the lithium supplementing effect of the LFO and the LNO at the same time of oxidation.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a positive electrode lithium supplementing additive, which has a core-shell structure, wherein the core body is Li 5 FeO 4 The shell is Li 2 NiO 2 The Li is 5 FeO 4 And Li (lithium) 2 NiO 2 The mass ratio of (2) is 4:5; the Li is 5 FeO 4 Particle diameter D of (2) 50 8 μm;
the preparation method of the positive electrode lithium supplementing agent comprises the following steps: li (Li) 5 FeO 4 With Li 2 NiO 2 And (3) co-sintering the precursor of the two under the nitrogen atmosphere at 600 ℃ for 20 hours to obtain the positive electrode lithium supplementing additive.
Example 2
The embodiment provides a positive electrode lithium supplementing additive, which has a core-shell structure, wherein the core body is Li 5 FeO 4 The shell is Li 2 NiO 2 The Li is 5 FeO 4 And Li (lithium) 2 NiO 2 The mass ratio of (2) to (6); the Li is 5 FeO 4 Particle diameter D of (2) 50 Is 5 mu m;
the preparation method of the positive electrode lithium supplementing agent comprises the following steps: li (Li) 5 FeO 4 With Li 2 NiO 2 And (3) co-sintering the precursor of the two under the argon atmosphere at 450 ℃ for 40 hours to obtain the positive electrode lithium supplementing additive.
Example 3
The embodiment provides a positive electrode lithium supplementing additive, which has a core-shell structure, wherein the core body is Li 5 FeO 4 The shell is Li 2 NiO 2 The Li is 5 FeO 4 And Li (lithium) 2 NiO 2 The mass ratio of (2) is 6:3; the Li is 5 FeO 4 Particle diameter D of (2) 50 Is 12 mu m;
the preparation method of the positive electrode lithium supplementing agent comprises the following steps:
Li 5 FeO 4 with Li 2 NiO 2 And (3) co-sintering the precursor of the two under the nitrogen atmosphere at 900 ℃ for 2 hours to obtain the positive electrode lithium supplementing additive.
Examples 4 to 5 are shown in Table 2, except Li 5 FeO 4 And Li (lithium) 2 NiO 2 The same as in example 1 was conducted except that the mass ratio of (C) was changed.
Examples 6 to 7 are shown in Table 3, except Li 5 FeO 4 Particle diameter D of (2) 50 Except for the variation, the rest was the same as in example 1.
Example 8 As shown in Table 4, except that the shell is Li 2 NiO 2 And carbon, the remainder being the same as in example 1; wherein the Li is 5 FeO 4 The mass ratio to carbon is 15:1.
Comparative example 1 as shown in table 6, the same as example 1 was conducted except that the positive electrode lithium supplement additive was not included in the case.
Application example 1
The application example provides a positive plate, which comprises a positive lithium supplementing agent, lithium iron phosphate, conductive carbon black and polyvinylidene fluoride in a mass ratio of 2:99:1.5:1;
the positive electrode lithium supplementing agent is the positive electrode lithium supplementing agent in the embodiment 1; the lithium iron phosphate has a particle diameter D 50 Nano lithium iron phosphate of 1.5 mu m;
the preparation method of the positive plate comprises the following steps:
mixing fresh positive electrode lithium supplementing agent and lithium iron phosphate according to the mass ratio of 2:99 in the example 1 to prepare active material mixing powder; conducting carbon black, N-methyl pyrrolidone and polyvinylidene fluoride with the mass ratio of 1.5:40:1 are dispersed and stirred at a high speed for 2 hours to prepare conducting slurry; and (3) mixing the active material powder and the conductive slurry at a high speed, stirring and mixing to prepare positive electrode slurry, scraping the prepared positive electrode slurry on an aluminum foil, drying for 20min at 120 ℃, rolling, and cutting to obtain the positive electrode plate.
Application examples 2 to 8 were the same as application example 1, except that the positive electrode lithium-supplementing agents described in corresponding fresh examples 2 to 8 were used, respectively.
Comparative application example 1 the same as application example 1 was conducted except that fresh positive electrode lithium-supplementing agent as described in comparative example 1 was used as shown in table 5.
Positive electrode sheet and silicon carbon negative electrode sheet, polyethylene diaphragm and 1mol/L LiPF provided in the above application examples and comparative application examples 6 Ec+dmc+emc electrolyte the 1Ah pouch cell was assembled according to the general process for preparing lithium ion cells.
Gram capacity test: adopting a Cheng Hong electric appliance Co., ltd battery performance test system (BTS 05/10C 8D-HP), respectively placing the prepared soft package batteries in a test cabinet for testing, and testing the discharge capacity of the batteries at 0.33C to obtain gram capacity; the batteries obtained by exposing the positive electrode lithium supplement in examples and comparative examples to air for one day were tested, and the measured gram capacity value was divided by the gram capacity of the fresh battery to obtain the stability of the positive electrode lithium supplement in air.
The test results are shown in tables 1 to 5:
TABLE 1
| Capacity (Ah) | Air stability (%) | |
| Application example 1 | 1.049 | 99.08 |
| Application example 2 | 1.043 | 99.52 |
| Application example 3 | 1.057 | 98.55 |
TABLE 2
TABLE 3 Table 3
| Li 5 FeO 4 Particle diameter D of (2) 50 (μm) | Capacity (Ah) | Air stability (%) | |
| Application example 1 | 8 | 1.049 | 99.08 |
| Application ofExample 6 | 3 | 1.030 | 96.60 |
| Application example 7 | 14 | 1.035 | 97.86 |
TABLE 4 Table 4
| Shell type | Capacity (Ah) | Air stability (%) | |
| Application example 1 | Li 2 NiO 2 | 1.049 | 99.08 |
| Application example 8 | Li 2 NiO 2 And carbon (C) | 1.048 | 99.53 |
TABLE 5
| Positive electrode lithium supplementing agent | Capacity (Ah) | Air stability (%) | |
| Application example 1 | LNO coated LFO | 1.049 | 99.08 |
| Comparative application example 1 | LFO | 1.041 | 94.03 |
From the above table, the following points can be seen:
(1) As can be seen from application examples 1 to 8, the positive electrode sheet provided by the invention has higher capacity exertion, and the positive electrode lithium supplementing agent has high capacity contribution rate; as can be seen from application examples 4 to 7, li 2 NiO 2 When the amount is small, LFO coating is not uniform, so that the air stability of the lithium supplementing agent is affected, and when Li 5 FeO 4 Particle diameter D of (2) 50 When the amount of the lithium ion-supplementing agent is small, the lithium ion-supplementing agent is liable to deteriorate, the capacity is poor, the air stability is low, and the particle diameter D 50 When the lithium ion battery is larger, the coating of the LNO is uneven, so that the lithium ion battery is easy to deteriorate, and the performance is correspondingly reduced; as can be seen from application example 8, the housing employs a set of LNO and CIn this case, the lithium supplementing effect of the positive electrode lithium supplementing agent can be improved as well.
(2) As is clear from application example 1 and comparative application example 1, LFOs that were not coated in application example 1 are susceptible to deterioration, and the stability in air is significantly reduced, and the capacity is reduced, compared with application example 1, whereas LFOs coated in application example 1 can avoid the above.
In summary, the invention provides the positive electrode lithium supplementing agent, the coating of the LNO can prevent the LFO from contacting with air, the stability of the LFO is improved, the capacity of the LFO can be exerted to the greatest extent, and the energy density and the cycle stability of the battery can be improved by utilizing the lithium supplementing effect of the LFO and the LNO.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (8)
1. The positive electrode lithium supplementing agent is characterized in that the positive electrode lithium supplementing agent is of a core-shell structure, wherein a core body comprises Li 5 FeO 4 The shell comprises Li 2 NiO 2 ；
The Li is 5 FeO 4 And Li (lithium) 2 NiO 2 The mass ratio of (1) to (10) is (1) to (10);
the Li is 5 FeO 4 Particle diameter D of (2) 50 From 5 μm to 12 μm.
2. The positive electrode lithium supplement of claim 1, wherein the shell further comprises carbon.
3. The positive electrode lithium-supplementing agent according to claim 2, wherein the Li 5 FeO 4 The mass ratio to carbon is (1 to 20): 1.
4. The positive plate is characterized by comprising a positive active material, a conductive agent, a binder and a positive lithium supplementing agent;
the positive electrode lithium-supplementing agent according to any one of claims 1 to 3.
5. The positive electrode sheet according to claim 4, wherein the mass ratio of the positive electrode lithium-supplementing agent, the positive electrode active material, the conductive agent, and the binder is (0.1 to 10): 90 to 99): 1 to 2): 1.
6. The positive electrode sheet according to claim 4, wherein the positive electrode active material comprises LiNi x Co y Mn 1-x-y O 2 And/or LiFePO 4 Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.2.
7. The positive electrode sheet according to claim 6, wherein the LiNi x Co y Mn 1-x-y O 2 In the form of a secondary sphere or a single crystal.
8. An electrochemical device, characterized in that the electrochemical device comprises the positive electrode sheet according to any one of claims 4 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210254003.2A CN114497514B (en) | 2022-03-15 | 2022-03-15 | Positive electrode lithium supplementing agent and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210254003.2A CN114497514B (en) | 2022-03-15 | 2022-03-15 | Positive electrode lithium supplementing agent and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114497514A CN114497514A (en) | 2022-05-13 |
| CN114497514B true CN114497514B (en) | 2023-07-14 |
Family
ID=81486184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210254003.2A Active CN114497514B (en) | 2022-03-15 | 2022-03-15 | Positive electrode lithium supplementing agent and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114497514B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115513457A (en) * | 2022-08-29 | 2022-12-23 | 深圳市德方创域新能源科技有限公司 | Positive electrode lithium supplement additive, preparation method thereof, positive electrode sheet, and secondary battery |
| CN115954453A (en) * | 2022-12-31 | 2023-04-11 | 湖北亿纬动力有限公司 | Positive electrode lithium supplement agent, lithium ion battery and formation method of positive electrode pre-lithiation |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102468695B1 (en) * | 2017-11-30 | 2022-11-21 | 주식회사 엘지에너지솔루션 | Formation method and formation apparatus of battery cell |
| KR20200127182A (en) * | 2018-03-02 | 2020-11-10 | 도다 고교 가부시끼가이샤 | Li-Ni composite oxide particle powder and non-aqueous electrolyte secondary battery |
| CN110299515B (en) * | 2018-03-23 | 2023-08-08 | 比亚迪股份有限公司 | Positive electrode active material, preparation method thereof, positive electrode and battery |
| CN110299496B (en) * | 2018-03-23 | 2021-09-21 | 比亚迪股份有限公司 | Battery diaphragm, power battery and vehicle |
| CN108878849B (en) * | 2018-07-04 | 2021-09-21 | 江西中汽瑞华新能源科技有限公司 | Synthesis process of lithium-rich oxide and lithium ion battery containing lithium-rich oxide |
| US20220190379A1 (en) * | 2019-03-29 | 2022-06-16 | Panasonic Intellectual Property Management Co., Ltd. | Lithium secondary battery |
| CN112490415B (en) * | 2019-09-12 | 2022-06-28 | 巴斯夫杉杉电池材料有限公司 | Lithium ion anode material lithium supplement additive and preparation method thereof |
| CN110867584B (en) * | 2019-11-04 | 2021-09-21 | 宁德新能源科技有限公司 | Lithium supplement material and positive electrode comprising same |
| KR20210156575A (en) * | 2020-06-18 | 2021-12-27 | 주식회사 엘지에너지솔루션 | Manufacturing method of positive electrode additives, positive electrode additives and positive electrode comprising the same |
| CN113178567A (en) * | 2021-03-29 | 2021-07-27 | 珠海冠宇电池股份有限公司 | Positive electrode lithium supplement material and lithium ion battery comprising same |
| CN113394393A (en) * | 2021-03-29 | 2021-09-14 | 珠海冠宇电池股份有限公司 | Positive electrode lithium supplement material and lithium ion battery comprising same |
| CN113471554A (en) * | 2021-07-06 | 2021-10-01 | 湖北亿纬动力有限公司 | Composite positive electrode lithium supplement additive and preparation method and application thereof |
| CN113903981A (en) * | 2021-09-27 | 2022-01-07 | 远景动力技术(江苏)有限公司 | Lithium-ion battery, preparation method and application thereof |
| CN113871600B (en) * | 2021-09-28 | 2023-07-21 | 联想(北京)有限公司 | Lithium ion positive electrode material, preparation method and application thereof |
| CN114122402A (en) * | 2021-11-16 | 2022-03-01 | 远景动力技术(江苏)有限公司 | Lithium ion battery positive electrode lithium supplement additive, positive plate, preparation method and application thereof |
| CN114094089B (en) * | 2021-11-26 | 2023-12-15 | 中南大学 | A kind of positive electrode lithium supplement additive and its preparation and application in lithium-ion batteries |
-
2022
- 2022-03-15 CN CN202210254003.2A patent/CN114497514B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| "核壳结构三元锂离子电池正极材料研究进展";李佳玮等;《材料导报》;第30卷;第187-190页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114497514A (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113036106A (en) | Composite lithium supplement additive and preparation method and application thereof | |
| CN111193018B (en) | Lithium battery positive electrode active material and preparation method and application thereof | |
| CN114497514B (en) | Positive electrode lithium supplementing agent and application thereof | |
| CN109841822A (en) | A kind of preparation method of the modified monocrystalline tertiary cathode material of lithium ion battery | |
| CN114079086A (en) | Positive electrode lithium supplement additive, positive electrode plate, preparation method of positive electrode plate and lithium ion battery | |
| CN114094068B (en) | Cobalt-coated positive electrode material, preparation method thereof, positive electrode plate and lithium ion battery | |
| CN113224278A (en) | Modified lithium ferric manganese phosphate material, preparation method and application thereof | |
| CN114122402A (en) | Lithium ion battery positive electrode lithium supplement additive, positive plate, preparation method and application thereof | |
| CN113782735A (en) | A kind of sodium ion battery cathode material, sodium ion battery and preparation method and electrical equipment | |
| CN115377485A (en) | Phosphate material and lithium ion battery | |
| CN114566646A (en) | Nickel-doped lithium manganese iron phosphate positive electrode material and preparation method and application thereof | |
| CN113889594A (en) | A kind of preparation method of boron-doped lanthanum zirconate lithium-coated graphite composite material | |
| CN114094060B (en) | Preparation method of high-voltage positive electrode material with core-shell structure | |
| CN111244563A (en) | Positive electrode lithium ion supplement additive and preparation method and application thereof | |
| US20250070164A1 (en) | Positive active material, positive electrode plate, lithium-ion battery, and electrical device | |
| EP4481856A1 (en) | Lithium iron phosphate positive electrode active material, preparation method therefor, and lithium ion battery | |
| CN113097453A (en) | Lithium pre-embedding method for positive electrode of lithium ion battery | |
| CN117117177A (en) | Battery cell | |
| CN114430031B (en) | Cobalt-free cathode material and preparation method and application thereof | |
| CN113130900A (en) | Vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material and preparation method thereof | |
| CN114455563A (en) | A kind of modified lithium iron phosphate material, preparation method and application thereof | |
| CN114784248A (en) | Coating modified high-nickel ternary cathode material, preparation method thereof and lithium ion battery | |
| CN114709413A (en) | Ternary material and application thereof | |
| CN116914293B (en) | Battery cell | |
| CN118754090B (en) | A positive electrode material precursor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |