CN114497514A - Positive electrode lithium supplement agent and application thereof - Google Patents
Positive electrode lithium supplement agent and application thereof Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention provides a positive electrode lithium supplement agent and application thereof5FeO4The housing comprises Li2NiO2. The invention adopts Li which is also taken as a lithium supplement agent2NiO2Coated Li5FeO4Avoidance of Li5FeO4Contact with air elevates Li5FeO4Environmental stability of (2), making Li5FeO4Can be exerted to the maximum extent, and Li2NiO2The lithium supplement effect is also achieved, and the energy density and the cycling stability of the battery can be improved by the aid of the lithium supplement effect of the lithium supplement device and the lithium supplement effect of the lithium supplement device.
Description
Technical Field
The invention belongs to the field of batteries, relates to a lithium supplement agent, and particularly relates to a positive electrode lithium supplement agent and application thereof.
Background
In the lithium ion battery, the lower side of the first coulombic efficiency of the positive electrode and the negative electrode determines the first efficiency of the whole battery, and when the positive electrode and the negative electrode are equivalent, the utilization rate of active lithium in the battery is the highest. The first efficiency of current commercial systems is limited by the lower first efficiency of the negative electrode. Therefore, much of the active Li supplied from the positive electrode is consumed, and the energy density of the battery as a whole is reduced.
Lithium ion supplement material Li widely studied at present5FeO4(LFO) is capable of releasing four equivalents of lithium ions, has a high theoretical capacity (726mAh/g), and is extremely poor in reversibility (coulombic efficiency)<10 percent) is a more ideal lithium supplement additive. However, LFO is unstable in air and tends to absorb moisture to form inactive LixFeyOzAnd residual alkali (Li)2CO3LiOH), which not only reduces its electrochemical activity, but the presence of residual alkali can also lead to gassing of the battery, causing safety hazards.
Based on the above research, it is necessary to provide a positive electrode lithium supplement agent, which has good stability, high theoretical capacity, and can improve the energy density and the cycling stability of the battery.
Disclosure of Invention
The invention aims to provide a positive electrode lithium supplement agent and application thereof, wherein the positive electrode lithium supplement agent is of a core-shell structure, a core body is LFO, and a shell with a lithium supplement effect wraps the LFO, so that the oxidation 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 the independent addition of the LFO is avoided.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a positive electrode lithium supplement agent, which is in a core-shell structure, wherein a core body comprises Li5FeO4The shell comprises Li2NiO2。
The invention uses Li as lithium-supplementing agent2NiO2(LNO) coated Li5FeO4Said LNO being capable of avoiding Li5FeO4Contact with air elevates Li5FeO4Environmental stability of (2), making Li5FeO4Can be exerted to the maximum extent, and Li2NiO2The lithium supplement effect is also achieved, and the energy density and the cycling stability of the battery can be improved by the aid of the lithium supplement effect of the lithium supplement device and the lithium supplement effect of the lithium supplement device.
Preferably, the housing further comprises carbon.
The shell also comprises conductive carbon, and the two coating materials can further coat Li5FeO4In the promotion of Li5FeO4The stability of the positive electrode is improved, and the conductivity of the positive electrode lithium supplement agent is improved.
Preferably, the Li5FeO4And Li2NiO2The mass ratio of (1 to 10) to (1 to 10) may be, for example, 1:1, 5:1, 10:1, 1:5 or 1:10, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the Li5FeO4The 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 values recited, and other values not recited in the numerical range are also applicable.
Core bodies of the invention Li5FeO4The mass ratio of the shell to the LiFePO is in a reasonable range4Excessive coating of the shell is not uniform, which can affect Li5FeO4Exertion of capacity, Li5FeO4When the amount is too small, the optimum lithium replenishing effect is not obtained.
Preferably, the Li5FeO4Particle diameter D of50Is 5 μm to 12 μm, for exampleAnd may be 5 μm, 8 μm, 10 μm, or 12 μm, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Li according to the invention5FeO4Particle diameter D of50The larger the particle size, the better the stability, but the particle size D50Too large will result in uneven LNO coating; particle size D of LFO50The smaller the specific surface area, the larger the area exposed to air, and the faster the lithium supplement agent deteriorates.
The preparation method of the anode lithium supplement agent comprises the following steps of Li5FeO4Precursors with Li2NiO2Precursors or of Li5FeO4With Li2NiO2Coating the precursors of the two;
the coating means includes blending or co-sintering.
Preferably, the precursor comprises any one of, or a combination of at least two of, a hydroxide, an oxide, an acetate or a carbonate of the corresponding metal, and typical, but non-limiting, combinations include a hydroxide and an oxide, an acetate and a carbonate, or a hydroxide and an acetate.
Preferably, the blending comprises dry blending or wet blending.
Preferably, the co-sintering temperature is from 450 ℃ to 900 ℃, for example 450 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃ or 900 ℃, but not limited to the recited values, and other values not recited in the numerical range 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 values not recited in the numerical range are equally applicable.
Preferably, the co-sintering atmosphere is argon and/or nitrogen.
The preferable preparation method of the positive electrode lithium supplement agent comprises Li5FeO4With Li2NiO2And co-sintering the precursors of the anode and the cathode to obtain the anode lithium supplement agent.
In a second aspect, the present invention provides a positive electrode sheet, comprising a positive electrode active material, a conductive agent, a binder, and a positive electrode lithium supplement agent;
the positive electrode lithium supplement agent is the positive electrode lithium supplement agent according to the first aspect.
Preferably, the mass ratio of the positive electrode lithium supplement agent, the positive electrode active material, the conductive agent and the binder is (0.1 to 10): (90 to 99): (1 to 2):1, and may be, for example, 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 enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the positive electrode active material includes LiNixCoyMn1-x-yO2And/or LiFePO4(lithium iron phosphate) where 0.5. ltoreq. x.ltoreq.0.9, for example 0.5, 0.7 or 0.9, 0. ltoreq. y.ltoreq.0.2, for example 0, 0.1 or 0.2, but not limited to the values listed, and other values not listed in the numerical range are likewise suitable.
Preferably, the LiNixCoyMn1-x-yO2The crystal is in a secondary spherical form or a single crystal form.
Preferably, said LiNi in the form of secondary spheresxCoyMn1-x-yO2Particle diameter D of509 μm to 25 μm, for example 9 μm, 10 μm, 15 μm, 20 μm or 25 μm, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, said LiNi in single crystal formxCoyMn1-x-yO2Particle diameter D of501.5 μm to 6 μm, and may be, for example, 1.5 μm, 2 μm, 3 μm, 4 μm, 5 μm or 6 μm, but is not limited to the values recited, and other values not recited in the numerical range are also applicable.
Preferably, the LiFePO4Including spherical lithium iron phosphate and/or nano lithium iron phosphate.
Preferably, the spherical lithium iron phosphate has a particle diameter D50Is 5 μm to 15 μm, and may be, for example, 5 μm, 8 μm, 10 μm, 13 μm or 15 μm, but is not limited to the values listed, and is not otherwise specified in the rangeThe same values apply.
Preferably, the particle size D of the nano lithium iron phosphate50Is 0.3 μm to 2.4. mu.m, and may be, for example, 0.3 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm or 2.4. mu.m, but is not limited to the values listed, and other values not listed in the numerical range are also 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 realized by adding Li into the lithium supplement agent5FeO4Surface coated with Li2NiO2Avoidance of Li5FeO4The problem that the capacity of the lithium secondary battery is affected by the deterioration of the lithium secondary battery in contact with air due to Li2NiO2Has better stability in the environment, is also a lithium supplement agent, and further inhibits Li5FeO4And during oxidation, the energy density and the cycling stability density of the battery can be improved by utilizing the lithium supplement effect of LFO and LNO.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. 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.
Example 1
The embodiment provides a lithium supplement additive for a positive electrode, wherein the lithium supplement additive for the positive electrode is of a core-shell structure, and a core body is Li5FeO4The shell is Li2NiO2The Li5FeO4And Li2NiO2The mass ratio of (A) to (B) is 4: 5; the Li5FeO4Particle diameter D of50Is 8 μm;
the preparation method of the positive electrode lithium supplement agent comprises the following steps: li5FeO4With Li2NiO2And co-sintering the precursors of the anode and the cathode at 600 ℃ for 20h in a nitrogen atmosphere to obtain the anode lithium supplement additive.
Example 2
The embodiment provides a lithium supplement additive for a positive electrode, wherein the lithium supplement additive for the positive electrode is of a core-shell structure, and a core body is Li5FeO4The shell is Li2NiO2The Li5FeO4And Li2NiO2The mass ratio of (A) to (B) is 2: 6; the Li5FeO4Particle diameter D of50Is 5 μm;
the preparation method of the positive electrode lithium supplement agent comprises the following steps: li5FeO4With Li2NiO2And co-sintering the precursors of the anode and the cathode for 40h at 450 ℃ in an argon atmosphere to obtain the anode lithium supplement additive.
Example 3
The embodiment provides a lithium supplement additive for a positive electrode, wherein the lithium supplement additive for the positive electrode is of a core-shell structure, and a core body is Li5FeO4The shell is Li2NiO2The Li5FeO4And Li2NiO2The mass ratio of (A) to (B) is 6: 3; the Li5FeO4Particle diameter D of50Is 12 μm;
the preparation method of the positive electrode lithium supplement agent comprises the following steps:
Li5FeO4with Li2NiO2And co-sintering the precursors of the anode and the cathode for 2h at 900 ℃ in a nitrogen atmosphere to obtain the anode lithium supplement additive.
Examples 4 to 5 are shown in Table 2, except for Li5FeO4And Li2NiO2The mass ratio of (3) was changed, and the rest was the same as in example 1.
Examples 6 to 7 are shown in Table 3, except for Li5FeO4Particle diameter D of50The procedure was as in example 1 except for the change.
Example 8 As shown in Table 4, except that the shell is Li2NiO2And carbon, the rest is the same as the embodiment 1; wherein, the Li5FeO4The mass ratio to carbon was 15: 1.
Comparative example 1 as shown in table 6, the same as example 1 was performed except that the positive electrode lithium supplement additive did not include a case.
Application example 1
The application example provides a positive plate, which comprises a positive electrode lithium supplement agent, lithium iron phosphate, conductive carbon black and polyvinylidene fluoride in a mass ratio of 2:99:1.5: 1;
the positive electrode lithium supplement agent is the positive electrode lithium supplement agent in the embodiment 1; the lithium iron phosphate has a particle size D501.5 mu m of nano lithium iron phosphate;
the preparation method of the positive plate comprises the following steps:
mixing the fresh positive electrode lithium supplement agent in the embodiment 1 with lithium iron phosphate in a mass ratio of 2:99 to prepare a mixed active material powder; dispersing and stirring conductive carbon black, N-methyl pyrrolidone and polyvinylidene fluoride in a mass ratio of 1.5:40:1 at a high speed for 2 hours to prepare conductive slurry; and stirring and mixing the mixed active substance powder and the conductive slurry at a high speed to prepare anode slurry, scraping and coating the prepared anode slurry on an aluminum foil, drying at 120 ℃ for 20min, rolling and cutting to obtain the anode sheet.
Application examples 2 to 8 were the same as in application example 1 except that the lithium replenishing agent for a positive electrode described in fresh examples 2 to 8 was used.
Comparative application example 1 the same procedure as in application example 1 was repeated except that the lithium replenishing agent for the positive electrode described in fresh comparative example 1 was used as shown in table 5.
The positive plate and the silicon-carbon negative plate, the polyethylene diaphragm and the 1mol/L LiPF provided by the application examples and the comparative application examples6And the/EC + DMC + EMC electrolyte is assembled into the 1Ah soft package battery according to the general process for preparing the lithium ion battery.
And (3) gram capacity test: respectively placing the prepared soft-package batteries in a test cabinet to test by adopting a battery performance test system (BTS05/10C8D-HP) of the Shenghong electric appliance corporation electric company, and testing the discharge capacity of the batteries at 0.33C to obtain gram capacity; the batteries obtained from the positive electrode lithium supplement agents of the examples and the comparative examples exposed in the 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 agent in the 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
| Li5FeO4Particle diameter D of50(μm) | Capacity (Ah) | Air stability (%) | |
| Application example 1 | 8 | 1.049 | 99.08 |
| Application example 6 | 3 | 1.030 | 96.60 |
| Application example 7 | 14 | 1.035 | 97.86 |
TABLE 4
| Type of shell | Capacity (Ah) | Air stability (%) | |
| Application example 1 | Li2NiO2 | 1.049 | 99.08 |
| Application example 8 | Li2NiO2And carbon | 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) from application examples 1 to 8, it can be seen that the positive electrode sheet provided by the invention has high capacity exertion, and the positive electrode lithium supplement agent has high capacity contribution rate; from application examples 4 to 7, it is clear that Li2NiO2When the amount is small, the LFO coating is not uniform, so that the air stability of the lithium supplement agent is influenced5FeO4Particle diameter D of50When the particle diameter D is smaller, the lithium-supplementing agent is liable to deteriorate, the capacity exertion is poor, the air stability is lowered50When the size is larger, the coating of LNO is not uniform, so that the lithium supplement agent is easy to deteriorate, and the performance is correspondingly reduced; as can be seen from application example 8, when a combination of LNO and C is used for the case, the lithium replenishing effect of the positive electrode lithium replenishing agent can be improved similarly.
(2) As is clear from application example 1 and comparative application example 1, the LFO uncoated in comparative application example 1 was easily deteriorated, stability in air was significantly lowered, and capacity was lowered, as compared with application example 1, which was avoided by the LFO coated in application example 1.
In summary, the present invention provides a lithium supplement agent for a positive electrode, in which the coating of LNO can prevent LFO from contacting air, so as to improve LFO stability, maximize LFO capacity, and improve battery energy density and cycle stability by using the lithium supplement effect of LFO and LNO.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. The positive electrode lithium supplement agent is characterized in that the positive electrode lithium supplement agent is of a core-shell structure, wherein a core body comprises Li5FeO4The shell comprises Li2NiO2。
2. The positive lithium supplement of claim 1, wherein the shell further comprises carbon.
3. The positive electrode lithium supplement of claim 1 or 2, wherein the Li is5FeO4And Li2NiO2The mass ratio of (1 to 10) to (1 to 10).
4. The positive electrode lithium supplement of claim 2, wherein the Li is5FeO4The mass ratio to carbon is (1 to 20): 1.
5. The positive electrode lithium supplement of claim 1 or 2, wherein the Li is5FeO4Particle diameter D of50Is 5 μm to 12 μm.
6. The positive plate is characterized by comprising a positive active material, a conductive agent, a binder and a positive lithium supplement agent;
the positive electrode lithium supplement agent is the positive electrode lithium supplement agent according to any one of claims 1 to 5.
7. The positive electrode sheet according to claim 6, wherein the mass ratio of the positive electrode lithium supplement agent, the positive electrode active material, the conductive agent and the binder is (0.1 to 10): (90 to 99): (1 to 2): 1.
8. The positive electrode sheet according to claim 6 or 7, wherein the positive electrode active material comprises LiNixCoyMn1-x-yO2And/or LiFePO4Wherein 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.
9. The positive electrode sheet according to claim 8, wherein said LiNixCoyMn1-x-yO2The crystal is in a secondary spherical form or a single crystal form.
10. An electrochemical device comprising the positive electrode sheet according to any one of claims 6 to 9.
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