CN114220951B - Positive electrode lithium supplementing additive and preparation method and application thereof - Google Patents
Positive electrode lithium supplementing additive and preparation method and application thereof Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a positive electrode lithium supplementing additive, a preparation method thereof, a positive electrode plate and a lithium ion battery. The positive electrode lithium supplementing additive has higher specific capacity and more lithium removing potential, so that lithium ions are easier to insert and remove, the conductivity is better, and the lithium supplementing 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 supplementing additive, and a preparation method and application thereof.
Background
In order to improve the energy density of lithium ion battery systems, scientific research institutions and battery enterprises try to introduce high-capacity negative electrode materials, such as alloyed silicon oxygen materials, into the negative electrode. However, these high-capacity anode materials undergo more irreversible reactions during the first lithium intercalation, which results in a decrease in the active lithium content in the full-cell system, and is not conducive to the improvement of the energy density of the system. In order to improve the first irreversible lithium loss, the current measures include pre-lithiation of the negative electrode material end, a negative electrode process lithium supplementing route, chemical pre-lithiation, electrochemical pre-lithiation and the like. The preparation cost of material prelithiation is high, and great potential safety hazards exist in the preparation process. And the lithium supplementing reagent such as lithium foil, lithium powder, lithium silicide powder and the like in the lithium supplementing route of the negative electrode process has high reactivity and large danger coefficient, and increases 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 has high environmental requirements, such as anaerobic, anhydrous and dry environments, which limit large-scale application. Chemical prelithiation is at experimental level, the prelithiation degree can be precisely controlled by controlling the reaction time, and the compatibility of the prelithiation reagent and the binder needs to be considered. The cleaning and subsequent assembly steps after prelithiation are air-labile and need to be performed under an inert atmosphere. Compared with the lithium supplementing modes of the cathodes, the lithium supplementing additive is added in the cathode slurry mixing process to pre-lithiate the cathode, and the cathode lithium supplementing additive has good compatibility with the existing battery production process and high safety and stability.
However, the existing lithium supplementing additive uses binary lithium with poor oxide conductivity and larger Li-O bond energy, so that Li release in the charging process is difficult, the lithium removing potential is increased, the kinetics of the lithium removing reaction is inhibited, and the lithium supplementing 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 positive electrode lithium supplementing additive has higher specific capacity and more lithium removing potential, so that lithium ions are easier to insert and remove, the conductivity is better, and the lithium supplementing effect is better.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the positive electrode lithium supplementing additive comprises a core material and an outer layer material coated on at least a part of the outer surface of the core material, wherein the core material is lithium oxide, the outer layer material is a lithium compound, the lithium compound contains nonmetallic elements, and the nonmetallic elements comprise one or more of phosphorus, sulfur or selenium.
The conductivity of the binary lithium oxide is poor, and the Li-O bond energy is large, 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 full play of the lithium supplementing effect is not facilitated. According to the invention, the surface of the lithium oxide is modified by phosphorus/sulfur/selenium or the binary lithium oxide is compounded with the phosphorus/sulfur/selenium structure of the lithium, so that the conductivity of the lithium oxide is improved, the release potential is reduced, and the release potential of lithium ions is reduced, so that the lithium ions are easier to insert and release, and the conductivity is better. Doping heterogeneous nonmetallic elements into metal oxides can have a significant impact on the electronic structure of the metal oxides, as heterogeneous nonmetallic elements differ from oxygen elements in terms of electronegativity, atomic radius, charge, spin sequence states, and the like. Compared with O element, S, P, se and other elements, the lithium sulfide, phosphide and selenide have weaker electronegativity, so that the lithium sulfide, phosphide and selenide have better conductivity. The Li-S, li-P and Li-Se bonds have smaller energy than Li-O bonds, contributing to improved polarization and lower delithiation potential of the lithium-compensating additive in the delithiation reaction. According to the invention, the doping of nonmetallic hetero-elements such as S, P, se into metal oxide can obviously optimize the conductivity and the reactivity of the oxide, and particularly, the doping of two hetero-elements or the compounding of a multiphase structure can play a remarkable synergistic effect, the lithium supplementing effect and the battery capacity can be greatly improved, and the advantages which are not possessed by a single hetero-element doping or single-phase structure can be displayed. When the lithium ion battery is used, the lithium ion battery can have good lithium supplementing effect and high lithium supplementing amount only by adding a small amount of the lithium ion battery into the positive electrode material. Wherein the chemical formula of the lithium compound can be Li x O a E b E=one of S/Se/P, and x/(a+b) =0.8 to 3.2; the chemical formula of the lithium compound may be Li x O a E b F c E and F are each one of S/Se/P, and x/(a+b+c) =0.8 to 3.4; the chemical formula of the lithium compound may be Li x E b E is one of S/Se/P, and x/b=0.8 to 4; the chemical formula of the lithium compound may be Li x E b -Li x F c E and F are each one of S/Se/P, and 0.8<x/b<4，0.8<x/c<4。
Preferably, the lithium oxide has the chemical formula Li x O y ，0.8<x/y<2.2. The lithium oxide may be a binary lithium oxide including Li 2 O 2 、Li 2 O。
Preferably, the nonmetallic element further includes a carbon element. The combination of carbon and lithium oxide or binary lithium oxide not only improves conductivity, inhibits the contact of the lithium oxide or binary lithium oxide with moisture in the air, but also enhances the stability of the composite structure.
The second object of the present invention is: aiming at the defects of the prior art, the preparation method of the positive electrode lithium supplementing additive is simple in steps, easy to operate and good in controllability.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the positive electrode lithium supplementing additive comprises the following steps:
and S1, placing the lithium oxide and non-metal element-containing material in a heating device, and introducing inert gas to heat and calcine 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 lithium oxide accounts for 0.2 to 70% of the molar ratio of the nonmetallic element, and preferably the lithium oxide accounts for 0.2 to 25% of the molar ratio of the nonmetallic element.
Preferably, the nonmetallic element-containing material comprises a precursor of carbon and a doped element material, and the weight part ratio of the oxide of lithium 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 and calcining are performed, the precursor of carbon and the oxide of lithium are heated and calcined to obtain a pre-product, and then the pre-product and the doped 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 doping 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 multiphase structure can play a remarkable synergistic effect, and the single heterogeneous element doping or the single-phase structure can show the advantages not possessed by the single heterogeneous element doping or the single-phase structure, 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 comprises the steps of placing the lithium oxide, the carbon precursor and the doping element material in the weight parts in a heating device, and introducing inert gas to heat and calcine the materials to obtain the positive electrode lithium supplement additive. The mutual dispersion, mixing or polymerization of the lithium oxide and the carbon precursor is helpful to promote conductivity, inhibit the contact of the lithium oxide or the binary lithium oxide with moisture in the air and enhance the stability of the composite structure. Compared with the 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 include two or more doping element materials, which are separately placed or mixed. Compared with mixed placement, the doped element materials are separately placed, so that the doped element materials flow to the lithium oxide under the drive of inert gas, the reaction is carried out, and the lithium supplementing effect of the prepared material is better.
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, the reaction is facilitated, the material reaction combination is firmer, and the lithium supplementing effect is better.
Preferably, the inert gas is argon or nitrogen, and the gas flow rate is 5 ml/min-50 ml/min. The inert gas can avoid 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 can affect the loss rate of the nonmetallic source, and is not excessive.
The third object of the present invention is to: aiming at the defects of the prior art, the anode material is provided with a small amount of lithium supplementing additive, can release a large amount of lithium, has a good lithium supplementing effect, effectively increases first effect and improves electrochemical performance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the positive electrode material comprises the positive electrode lithium supplementing additive.
The fourth object of the invention is that: aiming at the defects of the prior art, the positive plate can release a large amount of lithium for supplementing to the negative electrode, and reduces the lithium loss in the first lithium intercalation process of the negative electrode.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the positive plate comprises a positive current collector and a lithium supplementing additive arranged on at least one surface of the positive current collector, wherein the lithium supplementing additive is the positive lithium supplementing additive.
The fifth object of the present invention is: aiming at the defects of the prior art, the lithium ion battery has higher specific charge capacity, high initial efficiency and good electrochemical performance.
In order to achieve the above purpose, the present 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 supplementing additive has higher specific capacity and more lithium removing potential, so that lithium ions are easier to insert and remove, the conductivity is better, and the lithium supplementing effect is better.
Drawings
FIG. 1 is a schematic illustration of the invention with two dopant element materials separately placed in a tube furnace.
Fig. 2 is a schematic illustration of the mixed placement of two dopant elemental materials in a tube furnace according to the present invention.
Detailed Description
The 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 supplementing additive comprises a core material and an outer layer material coated on at least a part of the outer surface of the core material, wherein the core material is lithium oxide, the outer layer material is a lithium compound, the lithium compound contains nonmetallic elements, and the nonmetallic elements comprise phosphorus, sulfur or selenium.
2. A preparation method of a positive electrode lithium supplementing additive comprises the steps of adding 200g of binary lithium oxide Li 2 Placing O and 200g of graphene oxide in a tubular heating furnace, and Li 2 O is placed at the downstream, graphene oxide is placed at the upstream, inert gas Ar is introduced, the gas flow rate is 25ml/min, the heating and calcining temperature is set to 300 ℃, heating and reacting for 2h to obtain a mixture, 600g of doped 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 upstream positions of the tubular heating furnace, the mixture is placed at the downstream of the tubular heating furnace, inert gas Ar is introduced, the gas flow rate is 25ml/min, the heating and calcining temperature is set to 300 ℃, and the heating and reacting for 2h to obtain the positive electrode lithium supplement additive.
Example 2
The difference from example 1 is that: the heating and calcining temperature was 600 ℃.
The remainder is the same as in example 1 and will not be described again here.
Example 3
The difference from example 1 is that: the heating and calcining temperature was 500 ℃.
The remainder is the same as in example 1 and will not be described again 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 fig. 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 inert gas, a mixture (left side) of two doping element materials is placed at the middle of the heating pipe, the selenium source Se powder and the sulfur source (sulfur powder) of the two doping element materials are mixed and placed together, and binary lithium oxide (right side) is placed beside the heating pipe.
The remainder is the same as in example 1 and will not be described again 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 remainder is the same as in example 1 and will not be described again 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 respectively and separately placed at different upstream positions of a tubular heating furnace.
The remainder is the same as in example 1 and will not be described again here.
Example 7
The difference from example 1 is that: 200g of phosphorus source (red phosphorus) and 200g of sulfur source (sulfur powder) are respectively and separately placed at different upstream positions of a tubular heating furnace, as shown in fig. 1, a heating pipe and accessory 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 inert gas, two doping element materials and oxides of binary lithium are respectively and openly placed in the middle of the heating pipe, specifically, red phosphorus is arranged on the left side, sulfur powder is arranged in the middle of the heating pipe, and oxides of binary lithium are arranged on the right side of the heating pipe.
The remainder is the same as in example 1 and will not be described again here.
Example 8
The difference from example 1 is that: the gas flow rate was 10ml/min.
The remainder is the same as in example 1 and will not be described again here.
Example 9
The difference from example 1 is that: the gas flow rate was 40ml/min.
The remainder is the same as in example 1 and will not be described again here.
Example 10
The difference from example 1 is that: 200g of binary lithium oxide Li 2 O, 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 on 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 300 ℃, and the anode lithium supplement additive is obtained after heating and reacting for 2 hours.
The remainder is the same as in example 1 and will not be described again here.
Example 11
The difference from example 1 is that: 200g of binary lithium oxide Li 2 O, 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 on 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 300 ℃, the heating and reacting are carried out for 2 hours to obtain powder, and the powder and 200g of graphene oxide are mixed by using a commercially available mixing device to prepare the anode lithium supplement additive.
The remainder is the same as in example 1 and will not be described again here.
Example 12
The difference from example 1 is that: 600g of selenium source (Se powder) was added as a doping element material to a tube furnace.
The remainder is the same as in example 1 and will not be described again here.
Example 13
The difference from example 1 is that: 600g of a phosphorus source (red phosphorus) was charged as a doping element material in a tube furnace.
The remainder is the same as in example 1 and will not be described again here.
Comparative example 1: lithium ion batteries were prepared using a commercial lithium cobalt oxide pole piece.
Performance test: the positive electrode lithium supplement additives prepared in examples 1 to 13 and comparative example 1 were added to the positive electrode sheet at 1% by weight of the positive electrode active material, and the performance test was performed on the positive electrode sheet and the lithium ion battery, and the test results were recorded in table 1.
TABLE 1
As shown by the comparison of the table 1, compared with the prior art, the positive electrode lithium supplementing additive prepared by the invention has higher specific capacity and more lithium removing potential, so that lithium ions are easier to insert and remove, the conductivity is better, and the lithium supplementing effect is better. As is clear from the comparison between example 1 and comparative example 1, the charging capacity of the positive electrode active material can be increased by 2.2% by adding 1% by weight, which shows that the positive electrode lithium supplementing additive of the present invention has a remarkable lithium supplementing effect. As shown by comparison of examples 1-3, when the heating and calcining temperature is too high, the composite structure of sulfur/selenium/phosphide and sulfur/selenium/phosphide is easily generated by excessive deoxidation, so that the potential of lithium is increased, and the effect of lithium supplementing is poorer compared with that of doping in example 1. As shown in fig. 2, the lithium supplementing effect of the positive electrode lithium supplementing material prepared by separately placing nonmetallic sources is better than that of the positive electrode lithium supplementing material prepared by mixing and placing nonmetallic sources, as shown by comparison of examples 1, 4 and 5. As shown in fig. 1, the comparison of examples 1, 6 and 7 shows that when the doping element materials are respectively set to be 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 lithium supplementing additive is better. According to comparison of examples 1, 8 and 9, when the gas flow rate of the inert gas is set to be 25ml/min, the lithium supplementing effect of the prepared positive electrode lithium supplementing additive is better, because the gas flow rate is too high, the non-metal source is taken away by the inert gas to influence reaction combination, the gas flow rate is too low, the doping combination rate of the non-metal source is low, and the reaction effect is poor. As shown by comparison of examples 1, 10 and 11, when the lithium oxide is non-metal doped but not doped with carbon element or is directly and physically mixed with the carbon material, the prepared positive electrode lithium supplementing material has weak reaction kinetics and conductivity, and the lithium supplementing effect is poor. As shown by comparison of examples 1, 12 and 13, when the doping of two heterogeneous elements or the compounding of a multiphase structure can play a remarkable synergistic effect, the doping of a single heterogeneous element or the advantages not possessed by a single-phase structure can be displayed, and the prepared lithium supplementing additive has a better lithium supplementing effect.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (12)
1. The positive electrode lithium supplementing additive is characterized by comprising a core material and an outer layer material coated on at least a part of the outer surface of the core material, wherein the core material is lithium oxide, the outer layer material is a lithium compound or a compound of the lithium compound and carbon, the lithium compound contains nonmetallic elements, and the nonmetallic elements comprise one or more of phosphorus, sulfur or selenium;
wherein the chemical formula of the lithium compound is Li x E b -Li x F c E and F are each one of S, se and P, E and F are different and 0.8<x/b<4，0.8<x/c<4；
The chemical formula of the lithium oxide is Li x O y ，0.8<x/y<2.2。
2. The method for preparing the positive electrode lithium supplement additive according to claim 1, comprising the steps of: and (3) placing the lithium oxide and the non-metal element-containing material in a heating device, and introducing inert gas to heat and calcine the material to obtain the positive electrode lithium supplement additive.
3. The method for preparing the positive electrode lithium supplement additive according to claim 2, wherein the weight ratio of the lithium oxide to the nonmetallic element-containing material is 200-400:40-1200.
4. The method for preparing the positive electrode lithium supplementing additive according to claim 2, wherein the nonmetallic element-containing material comprises a precursor of carbon and a doped element material, and the weight part ratio of the oxide of lithium, the precursor of carbon and the doped element material is 200-400:100-300:40-1200.
5. The method for preparing a positive electrode lithium-supplementing additive according to claim 4, 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.
6. The method for preparing the positive electrode lithium supplement additive according to claim 5, wherein the method for preparing the positive electrode lithium supplement additive is characterized in that the lithium oxide, the carbon precursor and the doping element material in parts by weight are placed in a heating device, and inert gas is introduced into the heating device to heat and calcine the mixture to prepare the positive electrode lithium supplement additive.
7. The method for preparing a positive electrode lithium-supplementing additive according to claim 6, wherein the doping element materials include two or more kinds, and the doping element materials are placed separately or in a mixed state.
8. The method for preparing a positive electrode lithium-supplementing additive according to any one of claims 2, 6 or 7, wherein the heating and calcining temperature is 200 to 600 ℃ and the heating time is 0.5 to 20 hours.
9. The method for preparing a positive electrode lithium supplement additive according to any one of claims 2, 6 or 7, wherein the inert gas is argon or nitrogen, and the gas flow rate is 5ml/min to 50ml/min.
10. A positive electrode material comprising the positive electrode lithium supplement additive of claim 1.
11. A positive plate, comprising a positive current collector and a positive electrode material disposed on at least one surface of the positive current collector, wherein the positive electrode material is the positive electrode material of claim 10.
12. A lithium ion battery comprising the positive electrode sheet of claim 11.
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