CN116111072A - Positive electrode sodium supplement additive and preparation method and application thereof - Google Patents

Positive electrode sodium supplement additive and preparation method and application thereof Download PDF

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CN116111072A
CN116111072A CN202310201073.6A CN202310201073A CN116111072A CN 116111072 A CN116111072 A CN 116111072A CN 202310201073 A CN202310201073 A CN 202310201073A CN 116111072 A CN116111072 A CN 116111072A
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sodium
positive electrode
ion battery
additive
sodium ion
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杨雪
谢芳
张帅帅
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Shandong Haike Innovation Research Institute Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/36—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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/36—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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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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Abstract

The invention provides a positive electrode sodium supplement additive, and a preparation method and application thereof, and belongs to the technical field of sodium ion batteries. The invention adopts a liquid phase method and one-step sintering to synthesize the positive electrode sodium supplement additive C@Na x M y O z From sodium-rich metal compounds Na x M y O z The inner core and the carbon coating layer are composed of small particle size and supplementThe sodium effect is good, and the coating of the carbon layer can effectively improve the conductivity and air stability of the material and effectively inhibit the occurrence of adverse side reactions; when the active sodium ion battery is used for the positive electrode of the sodium ion battery, the active sodium ion battery can be compatible with the existing technology, the loss of active sodium ions is effectively compensated, the first charge capacity of the sodium ion battery is improved by more than 8%, and the effects of improving the coulomb efficiency and the circulation stability of the sodium ion battery are achieved.

Description

Positive electrode sodium supplement additive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a positive electrode sodium supplement additive, and a preparation method and application thereof.
Background
Sodium is an ideal substitute for lithium ion batteries due to its abundant resources, uniform global distribution, and similar physicochemical properties to lithium, and therefore, low-cost, high-performance sodium ion batteries are provided.
Similar to lithium ion batteries, the electrode materials of sodium ion batteries also have a problem of sodium loss in the electrochemical cycle, resulting in deterioration of their cycle performance. In order to solve the problems, sodium supplementing measures are adopted for the electrode material of the sodium ion battery.
The pre-sodium treatment method can be divided into positive pre-sodium treatment and negative pre-sodium treatment according to the different electrodes of the pre-sodium treatment. However, in view of the severe environmental requirements of sodium metal and organic solvents in the process of pre-sodifying the negative electrode, the electrochemical pre-sodifying operation is complex and difficult to apply on a large scale. In contrast, the positive electrode additive sodium supplementing method can be compatible with the pole piece preparation process of the existing sodium ion battery, is simple to operate and good in sodium supplementing effect, and has wide development prospect. The common positive electrode sodium supplement additive at present comprises Na 3 P、Na 2 O or Na 2 O 2 、Na 2 CO 3 Chain/cyclic sodium-containing carbon oxides (e.g. Na 2 C 2 O 4 、Na 2 C 4 O 4 、Na 2 C 6 O 6 、Na 2 CO 3 ) Etc., wherein Na 3 Although the capacity of P is higher, the P has toxicity and is not beneficial to mass production; na (Na) 2 O or Na 2 O 2 、Na 2 CO 3 The actual sodium supplementing capacity is small, and O 2 Generation can affect battery performance, such as CN 111293289a; the decomposition voltage of the chain/ring sodium-containing carbon oxide is higher, gas is generated in the charge and discharge process, the battery performance is affected, the capacity utilization rate of part of the carbon oxide is lower, and the sodium supplementing effect is poor.
CN113896240a discloses a compound for pre-sodium treatment and a preparation method thereof, which is used for the pre-sodium treatmentThe chemical formula of the compound is Na x M y O z Wherein x is more than or equal to 3 and less than or equal to 7, y is more than or equal to 1 and less than or equal to 2, z is more than or equal to 4 and less than or equal to 7, and M is one or more of Nb, ta or V. The compound is applied to a sodium ion battery, and in the battery charging process, the compound is irreversibly decomposed to release active sodium ions, so that the active sodium loss caused by growth of negative electrode SEI is supplemented, and the effects of improving the energy density and prolonging the cycle life of the sodium ion battery can be achieved. However, the sodium supplement agent disclosed in the patent is prepared by adopting a solid phase method, has larger particle size and wide distribution range, is not beneficial to the diffusion of sodium ions, and affects the sodium supplement effect. CN 111293290A discloses a sodium-rich transition metal oxide composite sodium-supplementing positive electrode active material, its sodium-supplementing additive is sodium-rich transition metal oxide, its chemical formula is Na x MO y The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is one or more of Ni, co, fe, mn, ru, ir, sn, cr, cu, nb, mo. The material adopts the mixture of two or more sodium supplementing materials as the positive electrode additive, can effectively compensate the active sodium loss of the sodium ion battery, but the material has poor conductivity and air stability of the sodium-rich metal oxide when being exposed to the air. Therefore, the development of simple and efficient sodium supplement additive has very important significance.
Disclosure of Invention
The invention provides a positive electrode sodium supplement additive, a preparation method and application thereof, wherein the obtained positive electrode sodium supplement additive is synthesized by adopting a liquid phase method and one-step sintering, and when the positive electrode sodium supplement additive is used for the positive electrode of a sodium ion battery, the positive electrode sodium supplement additive is compatible with the prior art, effectively compensates the loss of active sodium ions, and achieves the effect of improving the coulombic efficiency and the cycle stability of the sodium ion battery.
In order to achieve the aim, the invention provides an anode sodium supplement additive C@Na x M y O z From sodium-rich metal compounds Na x M y O z The core and the carbon coating layer, wherein M is at least one selected from Fe, ni, co, mn, cr, V, cu, zn, x is any integer of 1-6, y is any integer of 1-2, and z is any integer of 1-4.
Preferably, the sodium-rich metal compound has a core particle size of 1 to 10 μm and a carbon coating layer thickness of 5 to 15nm.
Preferably, the source of M is selected from at least one of the oxides, hydroxides, sulfates, chlorates, nitrates of M; wherein:
when M is Fe, it is selected from Fe 2 O 3 、Fe 3 O 4 、Fe(NO 3 ) 3 ·9H 2 O、FeCl 3 At least one of (a) and (b); preferably Fe (NO) 3 ) 3 ·9H 2 O；
When M is Ni, it is selected from NiO, ni (NO 3 ) 2 ·6H 2 O、NiSO 4 、NiCl 2 At least one of (a) and (b); preferably Ni (NO) 3 ) 2 ·6H 2 O；
When M is Co, it is selected from CoO, co (NO 3 ) 2 ·6H 2 O、CoSO 4 ·7H 2 O、CoCl 2 At least one of (a) and (b); co (NO) is preferred 3 ) 2 ·6H 2 O or CoCl 2 ；
When M is Mn, selected from MnO, mn (NO 3 ) 2 、MnSO 4 、MnCl 2 At least one of them.
Preferably, the source of sodium is selected from at least one of sodium oxide, hydroxide, peroxide, inorganic salt, and organic salt, and is selected from Na 2 O、NaOH、Na 2 CO 3 、NaNO 3 、Na 2 C 2 O 4 、CH 3 At least one of COONa, preferably NaNO 3 。
The invention also provides the positive electrode sodium supplement additive C@Na x M y O z The preparation method of (2) comprises the following steps:
uniformly dispersing an M source, a sodium source and a complexing agent into a solvent, and fully reacting at a certain temperature to obtain a precursor colloid;
spray drying the obtained precursor colloid to obtain precursor particles;
sintering the obtained precursor at high temperature in protective atmosphere to obtain the positive electrode sodium supplement additive C@Na x M y O z 。
Preferably, the complexing agent is at least one selected from citric acid, sodium gluconate, sodium alginate, polyvinylpyrrolidone and polyacrylic acid. It will be appreciated that the complexing agent may provide elemental carbon, which has both a complexing effect and a carbon source, with a dual effect.
Preferably, in the step of preparing the precursor colloid, the reaction temperature is 80-100 ℃ and the reaction time is 0.5-5 h;
in the step of preparing the precursor, the spray drying temperature is 150-250 ℃.
Preferably, the protective atmosphere is at least one selected from nitrogen, argon and helium;
the sintering temperature is 600-950 ℃, the sintering time is 1-20 h, and the heating rate is 1-20 ℃/min. It will be appreciated that in the above-described approach, prolonged high temperature sintering promotes grain growth, resulting in an increase in the final product particle size.
The invention also provides a positive plate of the sodium ion battery, which adopts the positive sodium supplement additive C@Na according to any one of the technical schemes x M y O z As a sodium supplementing additive, and homogenizing the sodium supplementing additive, a positive electrode active material, a conductive agent and a binder to prepare a positive electrode plate;
the addition amount of the sodium supplementing additive is 0.5-5% of the mass of the positive electrode active material.
The invention also provides a sodium ion battery, which comprises the positive plate of the sodium ion battery.
Preferably, the first-week charge specific capacity of the sodium ion battery is more than or equal to 135mAh/g, the first-week discharge specific capacity is more than or equal to 120mAh/g, and the capacity retention rate after 80 circles is more than or equal to 88 percent under the multiplying power of 0.1C.
Compared with the prior art, the invention has the advantages and positive effects that:
the positive electrode sodium supplement additive provided by the invention adopts a liquid phase method and a spray drying mode to prepare the sodium-rich metal compound (Na x M y O z ) The particle size of the obtained product is small, the particle size distribution range is narrow, and the diffusion particle size of sodium ions is effectively shortened;
the product is synthesized by one-step sintering, and the synthesis process is simple and efficient and has low energy consumption;
the positive electrode sodium supplement additive provided by the invention can effectively improve the conductivity and air stability of the material under the coating of the carbon layer, plays a role in stabilizing the interface between the material and the electrolyte, and effectively inhibits the occurrence of adverse side reactions;
the positive electrode sodium supplement additive provided by the invention has the advantages of lower decomposition potential and good sodium supplement effect, and only acts on the primary charging process, so that the subsequent circulation of the battery is not influenced; and when the active sodium ion battery is used for the positive electrode of the sodium ion battery, the active sodium ion battery can be compatible with the existing technology, the loss of active sodium ions is effectively compensated, the first charge capacity of the sodium ion battery is improved by more than 8%, and the effects of improving the coulomb efficiency and the cycle stability of the sodium ion battery are achieved.
Drawings
Fig. 1 is an SEM picture of the prepared sodium supplement additive provided in example 1 of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Precursor preparation
0.1mol of Fe (NO) 3 ) 3 ·9H 2 O is dissolved in 150mL deionized water and reacted for 0.5h at 85 ℃;
taking 0.525mol NaNO 3 Gradually adding the precursor colloid with 2g of polyvinylpyrrolidone into the ferric hydroxide solution under magnetic stirring, and reacting for 2 hours to obtain a precursor colloid;
and (3) carrying out spray drying on the precursor colloid, wherein the drying temperature is 200 ℃, and obtaining the precursor particles.
C@Na 5 FeO 4 Is prepared from
The precursor particles are heated for 2 hours in nitrogen atmosphere at 900 ℃ with the heating rate of 10 ℃/min to obtain C@Na 5 FeO 4 The SEM image is shown in fig. 1.
Battery assembly
Na is mixed with 3 V 2 (PO 4 ) 3 、5wt％C@Na 5 FeO 4 Uniformly mixing the sodium supplementing additive with the SuperP and the PVDF according to the proportion of 8:1:1, homogenizing, coating, drying and rolling to obtain a positive plate; preparing a negative electrode plate by adopting hard carbon as a negative electrode active material; and assembling the positive electrode plate and the negative electrode plate to obtain the sodium ion battery.
Example 2
Precursor preparation
0.1mol of Fe (NO) 3 ) 3 ·9H 2 O is dissolved in 150mL deionized water and reacted for 0.5h at 85 ℃;
taking 0.525mol NaNO 3 Gradually adding 0.035mol of citric acid into the ferric hydroxide solution under magnetic stirring, and reacting for 2 hours to obtain precursor colloid;
and (3) carrying out spray drying on the precursor colloid, wherein the drying temperature is 200 ℃, and obtaining the precursor particles.
C@Na 5 FeO 4 Is prepared from
The precursor particles are heated at 800 ℃ in nitrogen atmosphere with the heating rate of 10 ℃/min and the temperature is kept for 5 hours to obtain C@Na 5 FeO 4 。
Battery assembly
The procedure is as in example 1.
Example 3
Precursor preparation
0.1mol of Ni (NO) 3 ) 2 ·6H 2 O is dissolved in 150mL deionized water and reacted for 0.5h at 85 ℃;
taking 0.215mol NaNO 3 Gradually adding 0.0066mol sodium gluconate into the solution under magnetic stirring, and reacting at 85 ℃ for 2 hours to obtain a precursor colloid;
and (3) carrying out spray drying on the precursor colloid, wherein the drying temperature is 180 ℃, and obtaining precursor particles.
C@Na 2 NiO 2 Is prepared from
The precursor particles are heated for 3 hours in a nitrogen atmosphere at 850 ℃ at a heating rate of 10 ℃/min to obtain C@Na 2 NiO 2 。
Battery assembly
The procedure is as in example 1.
Example 4
Precursor preparation
0.1mol of Co (NO) 3 ) 2 ·6H 2 O is dissolved in 150mL deionized water and reacted for 0.5h at 85 ℃;
taking 0.215mol NaNO 3 Gradually adding 0.023mol sodium alginate into the solution under the action of magnetic stirring, and reacting for 2 hours at 85 ℃ to obtain precursor colloid;
and (3) carrying out spray drying on the precursor colloid, wherein the drying temperature is 180 ℃, and obtaining precursor particles.
C@Na 6 CoO 4 Is prepared from
The precursor particles are heated for 3 hours in a nitrogen atmosphere at 850 ℃ at a heating rate of 10 ℃/min to obtain C@Na 6 CoO 4 。
Battery assembly
The procedure is as in example 1.
Comparative example 1
The procedure is as in example 1, except that polyvinylpyrrolidone is not added during the mixing of the starting materials.
Comparative example 2
The procedure is as in example 3 except that sodium gluconate is not added during the mixing of the raw materials.
Comparative example 3
In comparison with example 1, the difference is that the C@Na prepared in example 1 is not added 5 FeO 4 The battery is composed of conventional raw materials only, and is specifically as follows:
na is mixed with 3 V 2 (PO 4 ) 3 Uniformly mixing (80 wt%), superP (10 wt%) and PVDF (10 wt%) and then homogenizing, coating, drying and rolling to obtain positive electrode plate; preparing a negative electrode plate by adopting hard carbon as a negative electrode active material; and assembling the positive electrode plate and the negative electrode plate to obtain the sodium ion battery.
Air stability test of sodium supplement
The sodium supplement agent in the above example 1, example 3 and comparative examples 1 and 2 was used as an active material, mixed with SP and PVDF in a ratio of 8:1:1 to prepare a pole piece, and a half cell was assembled with the sodium piece, and stability test was performed under conditions of 30% humidity and 30% temperature, and the data are shown in Table 1
TABLE 1
Examples 24h capacity retention (%)
Example 1 85.7
Example 3 84.3
Comparative example 1 55.2
Comparative example 2 56.8
As can be seen from the data in table 1, the carbon layer coating is effective in improving the air stability of the sodium-rich metal compound.
Full cell performance test
The sodium ion batteries prepared in the above examples and comparative examples were subjected to performance test under the condition of multiplying power of 0.1C, and the data are shown in table 2 below.
TABLE 2
Figure SMS_1
As shown in the table 2, the positive electrode sodium-supplementing additive can effectively supplement active sodium ions in the charging and discharging process, the added content is less than 5%, the first charge capacity of the sodium-ion battery can be improved by more than 8%, and the circulation stability is effectively improved.

Claims (10)

1. Positive electrode sodium supplement additive C@Na x M y O z Characterized by comprising a sodium-rich metal compound Na x M y O z The core and the carbon coating layer, wherein M is at least one selected from Fe, ni, co, mn, cr, V, cu, zn, x is any integer of 1-6, y is any integer of 1-2, and z is any integer of 1-4.
2. The positive electrode sodium supplement additive according to claim 1, wherein the sodium-rich metal compound has a core particle size of 1 to 10 μm and a carbon coating layer thickness of 5 to 15nm.
3. The positive electrode sodium supplement additive according to claim 1 or 2, wherein the source of M is selected from at least one of the group consisting of oxides, hydroxides, sulphates, chlorates, nitrates of M; wherein:
when M is Fe, it is selected from Fe 2 O 3 、Fe 3 O 4 、Fe(NO 3 ) 3 ·9H 2 O、FeCl 3 At least one of (a) and (b);
when M is Ni, it is selected from NiO, ni (NO 3 ) 2 ·6H 2 O、NiSO 4 、NiCl 2 At least one of (a) and (b);
when M is Co, it is selected from CoO, co (NO 3 ) 2 ·6H 2 O、CoSO 4 ·7H 2 O、CoCl 2 At least one of (a) and (b);
when M is Mn, selected from MnO, mn (NO 3 ) 2 、MnSO 4 、MnCl 2 At least one of them.
4. The positive electrode sodium supplement additive according to claim 1 or 2, wherein the sodium source is at least one selected from the group consisting of sodium oxides, hydroxides, peroxides, inorganic salts, and organic salts, and is selected from the group consisting of Na 2 O、NaOH、Na 2 CO 3 、NaNO 3 、Na 2 C 2 O 4 、CH 3 At least one of COONa, preferably NaNO 3 。
5. The positive electrode sodium supplement additive C@Na according to any one of claims 1 to 4 x M y O z The preparation method of (2) is characterized by comprising the following steps:
uniformly dispersing an M source, a sodium source and a complexing agent into a solvent, and fully reacting at a certain temperature to obtain a precursor colloid;
spray drying the obtained precursor colloid to obtain precursor particles;
sintering the obtained precursor at high temperature in protective atmosphere to obtain the positive electrode sodium supplement additive C@Na x M y O z 。
6. The preparation method of claim 5, wherein the complexing agent is at least one of citric acid, sodium gluconate, sodium alginate, polyvinylpyrrolidone and polyacrylic acid, and the coating layer accounts for 1-2% of the mass of the sodium-rich metal compound.
7. The method according to claim 5, wherein in the step of preparing the precursor colloid, the reaction temperature is 80 to 100 ℃ and the reaction time is 0.5 to 5 hours;
in the step of preparing the precursor, the spray drying temperature is 150-250 ℃;
the protective atmosphere is at least one selected from nitrogen, argon and helium;
the sintering temperature is 600-850 ℃, the sintering time is 5-20 h, and the heating rate is 1-20 ℃/min.
8. A positive plate of a sodium ion battery is characterized in that the positive sodium supplement additive C@Na as claimed in any one of claims 1 to 4 is adopted x M y O z As a sodium supplementing additive, and homogenizing the sodium supplementing additive, a positive electrode active material, a conductive agent and a binder to prepare a positive electrode plate;
the addition amount of the sodium supplementing additive is 0.5-5% of the mass of the positive electrode active material.
9. Sodium ion battery characterized by comprising a sodium ion battery positive electrode sheet according to claim 8.
10. The sodium ion battery of claim 9, wherein at a rate of 0.1C, the first week charge specific capacity of the sodium ion battery is greater than or equal to 135mAh/g, the first week discharge specific capacity is greater than or equal to 120mAh/g, and the capacity retention after 80 turns is greater than or equal to 88%.
CN202310201073.6A 2023-02-27 2023-02-27 Positive electrode sodium supplement additive and preparation method and application thereof Pending CN116111072A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116632220A (en) * 2023-07-21 2023-08-22 宁德时代新能源科技股份有限公司 Sodium supplementing material, preparation method thereof, positive electrode plate, electrode assembly, battery and electricity utilization device
CN117228745A (en) * 2023-11-10 2023-12-15 蜂巢能源科技股份有限公司 Sodium ion battery anode sodium supplementing agent and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116632220A (en) * 2023-07-21 2023-08-22 宁德时代新能源科技股份有限公司 Sodium supplementing material, preparation method thereof, positive electrode plate, electrode assembly, battery and electricity utilization device
CN117228745A (en) * 2023-11-10 2023-12-15 蜂巢能源科技股份有限公司 Sodium ion battery anode sodium supplementing agent and preparation method and application thereof
CN117228745B (en) * 2023-11-10 2024-01-23 蜂巢能源科技股份有限公司 Sodium ion battery anode sodium supplementing agent and preparation method and application thereof

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