CN114220951A - Positive electrode lithium supplement additive and preparation method and application thereof - Google Patents
Positive electrode lithium supplement additive and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a positive electrode lithium supplement additive, a preparation method thereof, a positive plate and a lithium ion battery. The positive electrode lithium supplement additive has higher specific capacity and more lithium removal potentials, so that lithium ions are easier to insert and remove, the conductivity is better, and the lithium supplement effect is better.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a positive electrode lithium supplement additive and a preparation method and application thereof.
Background
In order to increase the energy density of a lithium ion battery system, research institutes and battery enterprises try to introduce high-capacity cathode materials, such as alloyed silica materials, into the cathode. However, these high-capacity negative electrode materials undergo more irreversible reactions during the first lithium intercalation, which leads to a decrease in the active lithium content in the full-cell system, and is not favorable for increasing the energy density of the system. In order to improve the first irreversible lithium loss, the current measures include pre-lithiation at the end of a negative electrode material, a negative electrode process lithium supplement route, chemical pre-lithiation, electrochemical pre-lithiation and the like. The preparation cost of the material prelithiation is high, and great potential safety hazard exists in the preparation process. And lithium supplement reagents such as lithium foil, lithium powder, lithium silicide powder and the like in the lithium supplement route of the cathode process have high reaction activity and large risk coefficient, and increase the operation complexity and the environmental requirements. Electrochemical prelithiation is in a laboratory research stage, has the advantages of accurate control of prelithiation amount and good stability, but the high requirement on environment, such as oxygen-free, anhydrous and dry environment, limits the large-scale application of the electrochemical prelithiation. The chemical prelithiation is at an experimental level, the degree of prelithiation can be accurately controlled by controlling the reaction time, and the compatibility of the prelithiation reagent and the binder needs to be considered. The steps of cleaning and subsequent assembly after pre-lithiation are unstable to air and need to be carried out in an inert atmosphere. Compared with the lithium supplement mode of the cathodes, the lithium supplement additive is added in the slurry combination process of the anode to carry out pre-lithiation on the anode, and the method has good compatibility with the existing battery production process and high safety and stability.
However, the existing lithium supplement additive uses binary lithium oxide with poor conductivity and large Li-O bond energy, so that Li release in the charging process is difficult, the lithium removal potential is increased, the lithium removal reaction kinetics is inhibited, and the lithium supplement effect is not fully exerted.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the anode lithium supplement additive is provided, has higher specific capacity and more lithium removal potentials, and enables lithium ions to be more easily inserted and extracted, better conductivity and better lithium supplement effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the positive electrode lithium supplement additive comprises a core material and an outer layer material coated on at least one part of the outer surface of the core material, wherein the core material is an oxide of lithium, the outer layer material is a lithium compound, the lithium compound contains a non-metal element, and the non-metal element comprises one or more of phosphorus, sulfur or selenium.
Binary lithium oxide has poor conductivity and large Li-O bond energy, so that Li release is difficult in the charging process, the lithium removal potential is increased, the lithium removal reaction kinetics is inhibited, and the lithium supplement effect is not fully exerted. According to the invention, the surface phosphorus/sulfur/selenium modification is carried out on the lithium oxide or the binary lithium oxide is compounded with the phosphorus/sulfur/selenium structure of lithium, so that the conductivity of the lithium oxide is improved, the desorption potential is reduced, the release of oxygen is reduced, the desorption potential of lithium ions is reduced, the lithium ions are easier to insert and extract, and the conductivity is better. The electronic structure of the metal oxide is obviously affected by doping the heterogeneous non-metal element into the metal oxide, because the heterogeneous non-metal element is different from the oxygen element in electronegativity, atomic radius, charge, spin sequence state and other aspects. S, P, Se and the like are less electronegative than O, so that lithium sulfide, phosphide and selenide are better in conductivity. Compared with Li-O bonds, Li-S, Li-P and Li-Se bonds have smaller energy, which is helpful for improving the polarization of the lithium supplement additive in the lithium removal reaction and reducing the lithium removal potential. The invention discovers that the conductivity and the reactivity of the oxide can be obviously optimized by doping non-metal heterogeneous elements such as S, P, Se and the like into the metal oxide, particularly, doping two heterogeneous elements, orThe compounding of the multiphase structure can play an obvious synergistic effect, can greatly improve the lithium supplementing effect and the battery capacity, and can show the advantages that a single heterogeneous element is doped or a single-phase structure does not have. When the lithium ion battery is used, only a small amount of the lithium ion battery needs to be added into the anode material, so that the lithium ion battery has a good lithium supplement effect and high lithium supplement amount. Wherein the chemical formula of the lithium compound can be LixOaEbE is one of S/Se/P, and x/(a + b) is 0.8-3.2; the chemical formula of the lithium compound may be LixOaEbFcE and F are respectively one of S/Se/P, and x/(a + b + c) is 0.8-3.4; the chemical formula of the lithium compound may be LixEbE is one of S/Se/P, and x/b is 0.8-4; the chemical formula of the lithium compound may be LixEb-LixFcE and F are respectively one of S/Se/P, and 0.8<x/b<4，0.8<x/c<4。
Preferably, the lithium oxide has the formula LixOy，0.8<x/y<2.2. The lithium oxide may be a binary lithium oxide including Li2O2、Li2O。
Preferably, the non-metallic element further includes carbon element. The combination of carbon and lithium oxide or binary lithium oxide not only improves the conductivity, inhibits the contact of lithium oxide or binary lithium oxide with moisture in the air, and enhances the stability of the composite structure.
The second purpose of the invention is: aiming at the defects of the prior art, the preparation method of the anode lithium supplement additive is provided, and has the advantages of simple steps, easy operation and good controllability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a positive electrode lithium supplement additive comprises the following steps:
and S1, placing the lithium oxide and the non-metallic element-containing material in a heating device, introducing inert gas, heating and calcining to obtain the positive electrode lithium supplement additive.
Preferably, the weight part ratio of the lithium oxide to the nonmetallic element-containing material is 200-400: 40-1200. The molar ratio of the lithium oxide to the non-metal element is 0.2-70%, and preferably, the molar ratio of the lithium oxide to the non-metal element is 0.2-25%.
Preferably, the non-metallic element-containing material comprises a precursor of carbon and a doped element material, and the weight part ratio of the lithium oxide to the precursor of carbon to the doped element material is 200-400: 100-300: 40-1200. Preferably, the weight part ratio of the lithium oxide to the carbon precursor is 1-2: 0.2-12, and preferably, the weight part ratio of the lithium oxide to the carbon precursor is 1-2: 0.2-8.5. Preferably, when the heating calcination is performed, the precursor of carbon and the lithium oxide are heated and calcined to obtain a pre-product, and then the pre-product and the doping element material are heated and calcined to obtain the positive electrode lithium supplement additive.
Preferably, the doping element material comprises one or a mixture of more than two of a selenium source, a phosphorus source and a sulfur source. Preferably, the dopant element material comprises a mixture of two or more of a selenium source, a phosphorus source, and a sulfur source. Compared with one element doping, the doping of two heterogeneous elements or the compounding of a multi-phase structure can play an obvious synergistic effect, the advantages which are not possessed by single heterogeneous element doping or a single-phase structure can be displayed, and the prepared lithium ion battery has higher specific discharge capacity and electrochemical performance.
Preferably, the preparation method of the positive electrode lithium supplement additive is to place the lithium oxide, the carbon precursor and the doping element material in parts by weight in a heating device, and inject inert gas to heat and calcine the mixture to obtain the positive electrode lithium supplement additive. The lithium oxide and the carbon precursor are mutually dispersed, mixed or polymerized, which is helpful for improving the conductivity, inhibiting the contact of the lithium oxide or the binary lithium oxide with moisture in the air and enhancing the stability of the composite structure. Compared with mutual dispersion and mixing, the lithium oxide and the precursor of carbon are polymerized, so that the prepared material has better performance, better lithium supplementing effect and better conductivity.
Preferably, the doping element materials comprise more than two kinds, and the doping element materials are separately placed or mixed. Compared with mixed placement, the doped element material is separately placed, so that the doped element material flows to lithium oxide under the drive of inert gas, reaction is carried out, and the prepared material has a better lithium supplementing effect.
Preferably, the heating temperature is 200-600 ℃, and the heating time is 0.5-20 h. The proper heating temperature and heating time are controlled, which is beneficial to the reaction, so that the material reaction combination is firmer, and the lithium supplement effect is better.
Preferably, the inert gas is argon or nitrogen, and the gas flow rate is 5ml/min to 50 ml/min. The inert gas can avoid the oxidation and moisture reaction of the raw materials and the air, and the reaction quality and effect are influenced by the flow rate of the gas. The control of the inert gas flow rate may affect the loss rate of the non-metallic source and should not be too great.
The third purpose of the invention is that: aiming at the defects of the prior art, the cathode material is provided, has a small amount of lithium supplement additive, can release a large amount of lithium, has a good lithium supplement effect, effectively increases the first effect, and improves the electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the cathode material comprises the cathode lithium supplement additive.
The fourth purpose of the invention is that: aiming at the defects of the prior art, the positive plate can release a large amount of lithium to be supplemented to the negative electrode, and the lithium loss in the first lithium insertion process of the negative electrode is reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
the positive plate comprises a positive current collector and a lithium supplement additive arranged on at least one surface of the positive current collector, wherein the lithium supplement additive is the positive lithium supplement additive.
The fifth purpose of the invention is that: aiming at the defects of the prior art, the lithium ion battery is provided, and has the advantages of higher charging specific capacity, high first efficiency and good electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery comprises the positive plate.
Compared with the prior art, the invention has the beneficial effects that: the positive electrode lithium supplement additive has higher specific capacity and more lithium removal potentials, so that lithium ions are easier to insert and remove, the conductivity is better, and the lithium supplement effect is better.
Drawings
FIG. 1 is a schematic illustration of two separate dopant elemental materials of the present invention placed in a tubular furnace.
FIG. 2 is a schematic view of two doped elemental materials of the present invention mixed in a tubular furnace.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings, but the embodiments of the invention are not limited thereto.
Example 1
1. The positive electrode lithium supplement additive comprises a core material and an outer layer material coated on at least one part of the outer surface of the core material, wherein the core material is an oxide of lithium, the outer layer material is a lithium compound, the lithium compound contains a non-metal element, and the non-metal element comprises phosphorus, sulfur or selenium.
2. A method for preparing positive electrode lithium supplement additive comprises adding 200g binary lithium oxide Li2O and 200g of graphene oxide are placed in a tube furnace, Li2Placing O at the downstream, placing graphene oxide at the upstream, introducing inert gas Ar at the gas flow rate of 25ml/min, setting the heating and calcining temperature to be 300 ℃, heating and reacting for 2 hours to obtain a mixture, adding 600g of doping element materials into a tubular heating furnace, respectively and separately placing 200g of selenium source (Se powder), 200g of phosphorus source (red phosphorus) and 200g of sulfur source (sulfur powder) at different positions at the upstream of the tubular heating furnace, placing the mixture at the downstream of the tubular heating furnace, introducing inert gas Ar at the gas flow rate of 25ml/min, setting the heating and calcining temperature to be 300 ℃, and heating and reacting for 2 hours to obtain the anode lithium supplement additive.
Example 2
The difference from example 1 is that: the heating and calcining temperature was 600 ℃.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The difference from example 1 is that: the heating and calcining temperature was 500 ℃.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is that: 300g of selenium source (Se powder) and 300g of sulfur source (sulfur powder) are mixed and placed at the upstream of a tubular heating furnace, as shown in figure 2, a heating pipe and accessories are arranged in the middle of the tubular heating furnace, the left end of the heating pipe is an inlet end of inert gas, the right end of the heating pipe is an outlet end of the inert gas, a mixture (left side) of two doping element materials is placed in the middle of the heating pipe, the two doping element materials, namely selenium source Se powder and sulfur source (sulfur powder), are mixed and placed together, and binary lithium oxide (right side) is placed beside the mixture.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is that: 100g of selenium source (Se powder), 150g of phosphorus source (red phosphorus) and 200g of sulfur source (sulfur powder) were mixed and placed upstream of the tube furnace.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from example 1 is that: 100g of selenium source (Se powder), 150g of phosphorus source (red phosphorus) and 200g of sulfur source (sulfur powder) are separately placed at different positions on the upstream of the tubular heating furnace.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from example 1 is that: respectively and separately placing 200g of phosphorus source (red phosphorus) and 200g of sulfur source (sulfur powder) at different positions of the upstream of a tubular heating furnace, as shown in fig. 1, a heating pipe and an accessory are arranged in the middle of the tubular heating furnace, the left end of the heating pipe is an inlet end of inert gas, the right end of the heating pipe is an outlet end of the inert gas, the middle part of the heating pipe is respectively opened and placed with two doping element materials and binary lithium oxides, specifically, the left side is red phosphorus, the middle part is sulfur powder, and the right side is binary lithium oxide.
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from example 1 is that: the gas flow rate was 10 ml/min.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from example 1 is that: the gas flow rate was 40 ml/min.
The rest is the same as embodiment 1, and the description is omitted here.
Example 10
The difference from example 1 is that: 200g of binary lithium oxide Li2And respectively placing 200g of selenium source (Se powder), 200g of phosphorus source (red phosphorus) and 200g of sulfur source (sulfur powder) in different places at the upstream of a tubular heating furnace separately by using O and 600g of doping element material, introducing inert gas Ar, setting the heating and calcining temperature to be 300 ℃ and heating and reacting for 2 hours to obtain the anode lithium supplement additive, wherein the gas flow rate is 25 ml/min.
The rest is the same as embodiment 1, and the description is omitted here.
Example 11
The difference from example 1 is that: 200g of binary lithium oxide Li2O and 600g of doping element material, 200g of selenium source (Se powder), 200g of phosphorus source (red phosphorus) and 200g of sulfur source (sulfur powder) are respectively and separately placed at different positions at the upstream of a tubular heating furnace, inert gas Ar is introduced, the gas flow rate is 25ml/min, the heating and calcining temperature is set to be 300 ℃, the heating reaction is carried out for 2h to obtain powder, and the powder and 200g of graphene oxide are mixed by using a commercially available mixing device to obtain the anode lithium supplement additive.
The rest is the same as embodiment 1, and the description is omitted here.
Example 12
The difference from example 1 is that: 600g of selenium source (Se powder) was added as the doping element material in a tube furnace.
The rest is the same as embodiment 1, and the description is omitted here.
Example 13
The difference from example 1 is that: 600g of a phosphorus source (red phosphorus) was added as the doping element material in a tube furnace.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1: a lithium ion battery was prepared using commercial lithium cobaltate electrode sheets.
And (3) performance testing: the positive electrode lithium supplement additives prepared in examples 1 to 13 and comparative example 1 were added to the positive electrode sheet in an amount of 1% by weight of the positive electrode active material, and the positive electrode sheet and the lithium ion battery were prepared for performance testing, and the test results are reported in table 1.
TABLE 1
Compared with the prior art, the positive electrode lithium supplement additive prepared by the invention has higher specific capacity and more lithium removal potentials, so that lithium ions are easier to be inserted and extracted, the conductivity is better, and the lithium supplement effect is better. The comparison between example 1 and comparative example 1 shows that the charging capacity can be improved by 2.2% by adding 1% by weight of the positive electrode active material, which shows that the lithium supplementing effect of the positive electrode lithium supplementing additive of the present invention is significant. The comparison of examples 1-3 shows that when the heating and calcining temperature is too high, excessive deoxidation is easily caused to generate a sulfur/selenium/phosphide and a sulfur/selenium/phosphide composite structure, so that the potential of lithium is increased, and the lithium supplementing effect is poorer compared with the doping in example 1. From comparison among examples 1, 4 and 5, as shown in fig. 2, the positive electrode lithium supplement material prepared by separately placing the non-metal sources has better lithium supplement effect than that prepared by mixing the non-metal sources. From comparison among examples 1, 6 and 7, as shown in fig. 1, when the doping element materials are respectively set to 200g of selenium source (Se powder), 200g of phosphorus source (red phosphorus) and 200g of sulfur source (sulfur powder), the lithium supplementing effect of the prepared positive electrode added with lithium is better. The comparison of the embodiments 1, 8 and 9 shows that when the gas flow rate of the inert gas is set to be 25ml/min, the prepared positive electrode lithium supplement additive has better lithium supplement effect, because the gas flow rate is too fast, the non-metal source is taken away by the inert gas, the reaction combination is influenced, the gas flow rate is too slow, the doping combination rate of the non-metal source is low, and the reaction effect is poor. From comparison among examples 1, 10 and 11, when the lithium oxide is non-metal doped but not doped with carbon or directly physically mixed with a carbon material, the prepared positive electrode lithium supplement material has weak reaction kinetics and conductivity, and the lithium supplement effect is poor. From comparison among examples 1, 12 and 13, it is found that when doping of two heterogeneous elements or compounding of a multi-phase structure can achieve a significant synergistic effect, and can show advantages that doping of a single heterogeneous element or a single-phase structure does not have, the prepared lithium supplement additive has a better lithium supplement effect.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (14)
1. The positive electrode lithium supplement additive is characterized by comprising a core material and an outer layer material coated on at least one part of the outer surface of the core material, wherein the core material is an oxide of lithium, the outer layer material is a lithium compound, the lithium compound contains a non-metal element, and the non-metal element comprises one or more of phosphorus, sulfur or selenium.
2. The positive electrode lithium supplement additive according to claim 1, wherein the lithium oxide has a chemical formula of LixOy，0.8<x/y<2.2。
3. The positive electrode lithium supplement additive according to claim 1 or 2, wherein the non-metallic element further comprises carbon.
4. The method for preparing the lithium supplement additive for the positive electrode according to claim 1, comprising the steps of: and placing the lithium oxide and the material containing the non-metallic elements in a heating device, introducing inert gas, heating and calcining to obtain the anode lithium supplement additive.
5. The preparation method of the positive electrode lithium supplement additive according to claim 4, wherein the weight part ratio of the lithium oxide to the non-metallic element-containing material is 200-400: 40-1200.
6. The preparation method of the positive electrode lithium supplement additive according to claim 4, wherein the non-metallic element-containing material comprises a precursor of carbon and a doped element material, and the weight part ratio of the lithium oxide to the precursor of carbon to the doped element material is 200-400: 100-300: 40-1200.
7. The method for preparing the positive electrode lithium supplement additive according to claim 6, wherein the doping element material comprises one or a mixture of more than two of a selenium source, a phosphorus source and a sulfur source.
8. The method for preparing the positive electrode lithium supplement additive according to claim 7, wherein the method for preparing the positive electrode lithium supplement additive comprises the steps of placing the lithium oxide, the carbon precursor and the doping element material in parts by weight in a heating device, introducing inert gas, heating and calcining to obtain the positive electrode lithium supplement additive.
9. The method for preparing the lithium supplement additive for the positive electrode according to claim 8, wherein the doped elemental materials comprise two or more types, and the doped elemental materials are separately placed or mixed.
10. The preparation method of the positive electrode lithium supplement additive according to any one of claims 4, 8 or 9, wherein the heating temperature is 200-600 ℃ and the heating time is 0.5-20 h.
11. The method for preparing a lithium supplement additive for a positive electrode according to any one of claims 4, 8 or 9, wherein the inert gas is argon or nitrogen, and the gas flow rate is 5ml/min to 50 ml/min.
12. A positive electrode material comprising the positive electrode lithium supplement additive according to any one of claims 1 to 3.
13. A positive electrode sheet, comprising a positive electrode current collector and a positive electrode material disposed on at least one surface of the positive electrode current collector, wherein the positive electrode material is the positive electrode material according to claim 12.
14. A lithium ion battery comprising the positive electrode sheet according to claim 13.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114784268A (en) * | 2022-03-29 | 2022-07-22 | 中国科学院化学研究所 | Composite lithium supplement additive and lithium supplement method for lithium ion battery anode |
| CN115566288A (en) * | 2022-10-21 | 2023-01-03 | 无锡零一未来新材料技术研究院有限公司 | Lithium supplement additive and preparation method and application thereof |
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| CN115566288A (en) * | 2022-10-21 | 2023-01-03 | 无锡零一未来新材料技术研究院有限公司 | Lithium supplement additive and preparation method and application thereof |
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| CN114220951B (en) | 2023-09-05 |
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