CN114604904B - Preparation method and application of tellurium-doped lithium cobalt oxide precursor - Google Patents
Preparation method and application of tellurium-doped lithium cobalt oxide precursor Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 title abstract description 21
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 16
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000012716 precipitator Substances 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- CXXKWLMXEDWEJW-UHFFFAOYSA-N tellanylidenecobalt Chemical compound [Te]=[Co] CXXKWLMXEDWEJW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 4
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 4
- -1 tellurium anions Chemical class 0.000 claims abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 43
- 229910052744 lithium Inorganic materials 0.000 claims description 43
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 35
- 229910021529 ammonia Inorganic materials 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000010405 anode material Substances 0.000 description 12
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 10
- 235000019345 sodium thiosulphate Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005056 compaction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 150000001450 anions Chemical group 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical compound [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
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Abstract
The invention discloses a preparation method and application of a tellurium-doped lithium cobalt oxide precursor, wherein a cobalt salt solution, a precipitator and a complexing agent are added into a base solution for reaction, the precipitator is a mixed solution of tellurium dioxide dissolved in sodium hydroxide, the base solution is a mixed solution of ammonia water and thiosulfate, and when a reaction material reaches a target particle size, the reaction material is aged and subjected to solid-liquid separation to obtain the lithium cobalt oxide precursor. According to the method, tellurium is reduced into tellurium anions through thiosulfate, cobalt telluride is generated, and coprecipitate is formed with cobalt hydroxide, so that tellurium doping in the precursor is achieved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method and application of a tellurium-doped lithium cobalt oxide precursor.
Background
In the lithium ion positive electrode material, lithium cobaltate has higher working voltage and energy density, is easy to synthesize and can be rapidly charged and discharged, so that the lithium cobaltate is widely applied. In recent years, with further miniaturization and multifunctionality of electronic products, higher demands are being made on the energy density of battery output, and conventional lithium cobaltate has failed to meet the demands. On the premise of ensuring safety and proper circularity, the energy density of the lithium battery is improved, and the method is still the basic development direction of small lithium batteries in the next years.
The main ways to increase the energy density are: increasing the capacity of electrode materials and/or increasing the operating voltage of batteries, wherein increasing both voltage and capacity is currently the mainstay of the development of positive electrode materials for 3C lithium batteries. The working voltage of the existing lithium ion battery is basically between 3.0V and 4.3V, and when the lithium ion battery taking lithium cobaltate as the positive electrode material is charged to 4.5V, the capacity of the lithium ion battery can be increased by about 20 percent, but due to the self structure of the lithium cobaltate, when the charging voltage exceeds 4.2V, li 1-x CoO 2 The deintercalation coefficient x is more than or equal to 0.5, and the internal structure of the material collapses, so that a series of problems of poor charge and discharge circulation under high voltage, poor high-temperature storage performance and the like can be brought.
There is disclosed a high voltage lithium cobalt oxide positive electrode material having a compacted density of up to 4.1g/cm 3 -4.15g/cm 3 However, the particle size D50 is 17.0-19.0 μm, and in the lithium cobaltate industry, the particle with the particle size has a longer lithium ion diffusion path, so that the multiplying power performance of the particle needs to be improved, and in the charging and discharging process, the volume change inside the large particle easily causes microcracks of the material, so that the cycle performance of the particle is rapidly reduced. Most of lithium cobalt oxide materials in the current market are mainly in a polycrystalline shape, and the compaction density is 3.6g/cm 3 In the following, increasing the compaction density of lithium cobaltate material to increase its volumetric energy density is also an unprecedented problem.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a preparation method and application of a tellurium-doped lithium cobalt oxide precursor.
According to one aspect of the present invention, there is provided a method for preparing a lithium cobaltate precursor, comprising the steps of:
s1: adding cobalt salt solution, a precipitator and a complexing agent into base solution, and reacting under inert atmosphere, wherein the precipitator is a mixed solution of tellurium dioxide dissolved in sodium hydroxide, and the base solution is a mixed solution of ammonia water and thiosulfate;
s2: and (3) when the reaction material reaches the target particle size, aging the reaction material, and carrying out solid-liquid separation to obtain the lithium cobaltate precursor.
In some embodiments of the invention, in step S1, the cobalt salt solution is at least one of a solution of cobalt sulfate, cobalt nitrate, or cobalt chloride.
In some embodiments of the invention, in step S1, the concentration of the cobalt salt solution is 1.0-2.0mol/L.
In some embodiments of the present invention, in step S1, the concentration of sodium hydroxide in the precipitant is 2.0-4.0mol/L, and the tellurium dioxide is added in an amount of 1-10% of the molar amount of sodium hydroxide.
In some embodiments of the invention, in step S1, the complexing agent is 6.0-12.0mol/L ammonia.
In some embodiments of the invention, in step S1, the pH of the base solution is 10-11, the ammonia concentration is 5-10g/L, and the thiosulfate concentration in the base solution is 0.1-3.0mol/L.
In some embodiments of the invention, in step S1, the temperature of the reaction is controlled to be 55-65 ℃, the pH is 10-11, and the ammonia concentration is 5-10g/L.
In some embodiments of the invention, in step S1, the reaction is performed in a reaction vessel, and the volume of the base solution is 8-12% of the volume of the reaction vessel.
In some embodiments of the invention, in step S1, the reaction is carried out at a stirring speed of 200-500 r/min.
In some embodiments of the invention, in step S2, the aging time is 24-48 hours.
In some embodiments of the invention, in step S2, the target particle size D50 of the reaction mass is 2.0-5.0 μm.
In some embodiments of the present invention, step S2 further comprises washing and drying the solid phase after the solid-liquid separation, optionally, the drying temperature is 100-120 ℃, and the drying time is 4-6 hours.
The invention also provides application of the lithium cobaltate precursor in preparation of lithium cobaltate. In some embodiments of the invention, the method of preparing lithium cobaltate comprises: mixing the lithium cobaltate precursor with a lithium source, and roasting in an oxygen atmosphere to obtain the lithium cobaltate. By doping tellurium, the precursor is reduced and synthesized, and sintered at low temperature, so that the long-cycle and high-compaction monocrystal lithium cobalt oxide anode material is obtained.
In some embodiments of the invention, the lithium source is at least one of lithium carbonate or lithium hydroxide.
In some embodiments of the invention, the firing temperature is 700-800 ℃. Further, the roasting time is 12-18h.
In some embodiments of the invention, the molar ratio of cobalt element in the lithium cobaltate precursor to lithium element in the lithium source is 1: (1.0-1.2).
The invention also provides application of the lithium cobaltate precursor prepared by the preparation method in preparation of the lithium ion battery anode material.
The invention also provides application of the lithium cobaltate precursor prepared by the preparation method in preparation of lithium ion batteries.
According to a preferred embodiment of the invention, there is at least the following advantageous effect:
1. according to the method, cobalt salt, complexing agent and precipitant are used for coprecipitation reaction, and tellurium doping is carried out, so that tellurium-doped cobalt hydroxide is obtained, and because the tellurate is soluble and is difficult to carry out the coprecipitation reaction with cobalt, tellurium is reduced into tellurium anions through thiosulfate to generate cobalt telluride, and a coprecipitate is formed with the cobalt hydroxide, so that tellurium doping in a precursor is achieved, and the reaction equation is as follows:
4Co 2+ +4TeO 3 2- +3S 2 O 3 2- +6OH - ＝4CoTe↓+6SO 4 2- +3H 2 O；
Co 2+ +2OH - ＝Co(OH) 2 ↓。
2. the cobalt oxide can change the crystal phase to lead the whisker to be thinned, and the material is loose and porous, so that the reaction is always in a reducing atmosphere in the coprecipitation process, the cobalt oxidation is avoided, the generated precursor is more compact, and the lithium cobalt oxide material produced by subsequent sintering has higher compaction density.
3. The lithium cobalt oxide precursor prepared by the method is calcined with a lithium source to obtain the tellurium-doped lithium cobalt oxide anode material. Tellurium doping is used to replace oxygen atoms in lithium cobaltate, and in the subsequent sintering process, cobalt telluride is gradually oxidized in oxygen (CoTe+2O 2 ＝CoTeO 4 ) As an anion group, the tellurium-doped lithium ion battery can further stabilize a crystal skeleton, has larger ionic radius, further enlarges interlayer spacing, improves the accommodation amount of lithium, and further improves the specific capacity of the material.
4. The doping of tellurium is different from the doping of other elements, the tellurium is used as a nonmetallic element, stable anion groups can be formed, sulfur and selenium of the same family are extremely volatile after being oxidized at high temperature, impurity removal is difficult, and tellurium can exist stably.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is an SEM image of lithium cobalt oxide prepared according to example 1 of the invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The tellurium-doped lithium cobalt oxide anode material is prepared by the embodiment, and the specific process is as follows:
step 1, preparing a cobalt sulfate solution with the concentration of 1.0 mol/L;
step 2, preparing a sodium hydroxide solution with the concentration of 2.0mol/L as a precipitator, and adding tellurium dioxide with the molar quantity of 1% of sodium hydroxide until the tellurium dioxide is completely dissolved to obtain a mixed solution;
step 3, preparing ammonia water with the concentration of 6.0mol/L as a complexing agent;
step 4, adding a base solution into the reaction kettle, introducing nitrogen, wherein the volume of the base solution accounts for 12% of the volume of the reaction kettle, controlling the pH of the base solution to be 11 and the ammonia concentration to be 10g/L, and adding sodium thiosulfate to enable the sodium thiosulfate concentration in the base solution to be 0.1mol/L;
step 5, adding the cobalt sulfate solution prepared in the step 1, the mixed solution prepared in the step 2 and the ammonia water prepared in the step 3 into a reaction kettle in parallel to react, and controlling the stirring speed of the reaction kettle to be 200r/min, the pH value to be 11, the temperature in the kettle to be 55 ℃ and the ammonia concentration to be 10g/L;
step 6, stopping feeding and aging for 24 hours when the D50 of the materials in the reaction kettle is detected to reach 2.0 mu m;
step 7, carrying out solid-liquid separation on the materials in the kettle, washing the precipitate by using pure water, and drying for 6 hours at 100 ℃ to obtain a lithium cobaltate precursor material;
and 8, mixing the precursor material obtained in the step 7 with lithium carbonate according to the molar ratio of cobalt element to lithium element of 1:1, roasting in an oxygen atmosphere at the temperature of 700 ℃ for 18 hours, and crushing, sieving and removing iron to obtain the tellurium-doped lithium cobalt oxide anode material.
Fig. 1 is an SEM image of lithium cobaltate prepared in this example, from which it can be seen that the material is a very dense bulk structure.
Example 2
The tellurium-doped lithium cobalt oxide anode material is prepared by the embodiment, and the specific process is as follows:
step 1, preparing a cobalt nitrate solution with the concentration of 1.5mol/L;
step 2, preparing a sodium hydroxide solution with the concentration of 3.0mol/L as a precipitator, and adding tellurium dioxide with the molar quantity of 5% of sodium hydroxide until the tellurium dioxide is completely dissolved to obtain a mixed solution;
step 3, preparing ammonia water with the concentration of 9.0mol/L as a complexing agent;
step 4, adding a base solution into the reaction kettle, introducing nitrogen, wherein the volume of the base solution accounts for 10% of the volume of the reaction kettle, controlling the pH of the base solution to be 10.5 and the ammonia concentration to be 8g/L, and adding sodium thiosulfate to enable the sodium thiosulfate concentration in the base solution to be 1.5mol/L;
step 5, adding the cobalt nitrate solution prepared in the step 1, the mixed solution prepared in the step 2 and the ammonia water prepared in the step 3 into a reaction kettle in parallel to react, and controlling the stirring speed of the reaction kettle to be 350r/min, the pH value to be 10.5, the temperature in the kettle to be 58 ℃ and the ammonia concentration to be 8g/L;
step 6, stopping feeding and aging for 36 hours when the D50 of the materials in the reaction kettle is detected to reach 3.5 mu m;
step 7, carrying out solid-liquid separation on the materials in the kettle, washing the precipitate by using pure water, and drying for 5 hours at 110 ℃ to obtain a lithium cobaltate precursor material;
and 8, mixing the precursor material obtained in the step 7 with lithium hydroxide according to the mol ratio of cobalt element to lithium element of 1:1.1, roasting in an oxygen atmosphere at the roasting temperature of 750 ℃ for 15 hours, and crushing, sieving and removing iron to obtain the tellurium-doped lithium cobalt oxide anode material.
Example 3
The tellurium-doped lithium cobalt oxide anode material is prepared by the embodiment, and the specific process is as follows:
step 1, preparing cobalt chloride solution with the concentration of 2.0 mol/L;
step 2, preparing a sodium hydroxide solution with the concentration of 4.0mol/L as a precipitator, and adding tellurium dioxide with the molar quantity of 10% of sodium hydroxide until the tellurium dioxide is completely dissolved to obtain a mixed solution;
step 3, preparing ammonia water with the concentration of 12.0mol/L as a complexing agent;
step 4, adding a base solution into the reaction kettle, introducing argon, controlling the pH of the base solution to be 10 and the ammonia concentration to be 5g/L, and adding sodium thiosulfate to enable the sodium thiosulfate concentration in the base solution to be 3.0mol/L, wherein the volume of the base solution accounts for 12% of that of the reaction kettle;
step 5, adding the cobalt chloride solution prepared in the step 1, the mixed solution prepared in the step 2 and the ammonia water prepared in the step 3 into a reaction kettle in parallel to react, and controlling the stirring speed of the reaction kettle to be 500r/min, the pH value to be 10, the temperature in the kettle to be 65 ℃ and the ammonia concentration to be 5g/L;
step 6, stopping feeding and aging for 48 hours when the D50 of the materials in the reaction kettle is detected to reach 5.0 mu m;
step 7, carrying out solid-liquid separation on the materials in the kettle, washing the precipitate by using pure water, and drying for 4 hours at 120 ℃ to obtain a lithium cobaltate precursor material;
and 8, mixing the precursor material obtained in the step 7 with lithium hydroxide according to the molar ratio of cobalt element to lithium element of 1:1.2, roasting in an oxygen atmosphere at the roasting temperature of 800 ℃ for 12 hours, and crushing, sieving and removing iron to obtain the tellurium-doped lithium cobalt oxide anode material.
Comparative example 1
This comparative example prepared a lithium cobaltate cathode material, differing from example 1 in that tellurium dioxide and sodium thiosulfate were not added, specifically by the following procedure:
step 1, preparing a cobalt sulfate solution with the concentration of 1.0 mol/L;
step 2, preparing a sodium hydroxide solution with the concentration of 2.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 6.0mol/L as a complexing agent;
step 4, adding a base solution into the reaction kettle, introducing nitrogen, wherein the volume of the base solution is 12% of the volume of the reaction kettle, and controlling the pH value of the base solution to be 11 and the ammonia concentration to be 10g/L;
step 5, adding the cobalt sulfate solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2 and the ammonia water prepared in the step 3 into a reaction kettle in parallel to react, and controlling the stirring speed of the reaction kettle to be 200r/min, the pH value to be 11, the temperature in the kettle to be 55 ℃ and the ammonia concentration to be 10g/L;
step 6, stopping feeding and aging for 24 hours when the D50 of the materials in the reaction kettle is detected to reach 2.0 mu m;
step 7, carrying out solid-liquid separation on the materials in the kettle, washing the precipitate by using pure water, and drying for 6 hours at 100 ℃ to obtain a lithium cobaltate precursor material;
and 8, mixing the precursor material obtained in the step 7 with lithium carbonate according to the molar ratio of cobalt element to lithium element of 1:1, roasting in an oxygen atmosphere at the temperature of 700 ℃ for 18 hours, and crushing, sieving and removing iron to obtain the lithium cobalt oxide anode material.
Comparative example 2
The lithium cobaltate cathode material prepared in this example is different from that in example 2 in that tellurium dioxide and sodium thiosulfate are not added, and the specific process is as follows:
step 1, preparing a cobalt nitrate solution with the concentration of 1.5mol/L;
step 2, preparing sodium hydroxide solution with the concentration of 3.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 9.0mol/L as a complexing agent;
step 4, adding a base solution into the reaction kettle, introducing nitrogen, wherein the volume of the base solution accounts for 10% of the volume of the reaction kettle, and controlling the pH of the base solution to be 10.5 and the ammonia concentration to be 8g/L;
step 5, adding the cobalt nitrate solution prepared in the step 1, the mixed solution prepared in the step 2 and the ammonia water prepared in the step 3 into a reaction kettle in parallel to react, and controlling the stirring speed of the reaction kettle to be 350r/min, the pH value to be 10.5, the temperature in the kettle to be 58 ℃ and the ammonia concentration to be 8g/L;
step 6, stopping feeding and aging for 36 hours when the D50 of the materials in the reaction kettle is detected to reach 3.5 mu m;
step 7, carrying out solid-liquid separation on the materials in the kettle, washing the precipitate by using pure water, and drying for 5 hours at 110 ℃ to obtain a lithium cobaltate precursor material;
and 8, mixing the precursor material obtained in the step 7 with lithium hydroxide according to the mol ratio of cobalt element to lithium element of 1:1.1, roasting in an oxygen atmosphere at the roasting temperature of 750 ℃ for 15 hours, and crushing, sieving and removing iron to obtain the lithium cobaltate anode material.
Comparative example 3
The lithium cobaltate cathode material prepared in this example is different from that in example 3 in that tellurium dioxide and sodium thiosulfate are not added, and the specific process is as follows:
step 1, preparing cobalt chloride solution with the concentration of 2.0 mol/L;
step 2, preparing a sodium hydroxide solution with the concentration of 4.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 12.0mol/L as a complexing agent;
step 4, adding a base solution into the reaction kettle, introducing argon, wherein the volume of the base solution accounts for 12% of the volume of the reaction kettle, and controlling the pH of the base solution to be 10 and the ammonia concentration to be 5g/L;
step 5, adding the cobalt chloride solution prepared in the step 1, the mixed solution prepared in the step 2 and the ammonia water prepared in the step 3 into a reaction kettle in parallel to react, and controlling the stirring speed of the reaction kettle to be 500r/min, the pH value to be 10, the temperature in the kettle to be 65 ℃ and the ammonia concentration to be 5g/L;
step 6, stopping feeding and aging for 48 hours when the D50 of the materials in the reaction kettle is detected to reach 5.0 mu m;
step 7, carrying out solid-liquid separation on the materials in the kettle, washing the precipitate by using pure water, and drying for 4 hours at 120 ℃ to obtain a lithium cobaltate precursor material;
and 8, mixing the precursor material obtained in the step 7 with lithium hydroxide according to the mol ratio of cobalt element to lithium element of 1:1.2, roasting in an oxygen atmosphere at the roasting temperature of 800 ℃ for 12 hours, and crushing, sieving and removing iron to obtain the lithium cobaltate anode material.
TABLE 1 detection of compaction Density
| Density of compaction g/cm 3 | |
| Example 1 | 4.23 |
| Example 2 | 4.21 |
| Example 3 | 4.25 |
| Comparative example 1 | 3.81 |
| Comparative example 2 | 3.76 |
| Comparative example 3 | 3.83 |
Test examples
The lithium cobaltate material obtained in the examples and the comparative examples is prepared by weighing active material, conductive agent and binder in a ratio of 92:4:4 by taking acetylene black as conductive agent and PVDF as binder, adding a certain amount of organic solvent NMP, stirring, coating on aluminum foil to prepare a positive plate, adopting a metal lithium plate as a negative electrode, and preparing the CR2430 button cell in a glove box filled with argon. The electrical performance test was performed on a CT2001A type blue electrical test system. Test conditions: the test temperature of 3.0-4.48V, current density 1 C=180 mAh/g is 25+ -1 ℃. The test results are shown in Table 2.
TABLE 2 electrochemical Properties of lithium cobalt oxide
As can be seen from table 2, the discharge capacity and the cycle performance of the comparative example are significantly lower than those of the examples, because tellurium dioxide and sodium thiosulfate are added in the examples, the cobalt telluride generated is oxidized in the sintering process, and is used as an anion group, so that the crystal skeleton can be stabilized, and tellurium has a larger ionic radius, the interlayer spacing is enlarged, the lithium containing amount is increased, and the specific capacity and the cycle performance of the material are further improved. While it can be seen from table 1 that the compaction density is also higher for the examples, with higher volumetric energy density.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (5)
1. The preparation method of the lithium cobaltate precursor is characterized by comprising the following steps of:
s1: adding cobalt salt solution, a precipitator and a complexing agent into base solution, and reacting under inert atmosphere, wherein the precipitator is a mixed solution of tellurium dioxide dissolved in sodium hydroxide, and the base solution is a mixed solution of ammonia water and thiosulfate; the concentration of sodium hydroxide in the precipitant is 2.0-4.0mol/L, and the adding amount of tellurium dioxide is 1-10% of the molar amount of sodium hydroxide; the pH value of the base solution is 10-11, the ammonia concentration is 5-10g/L, and the concentration of thiosulfate in the base solution is 0.1-3.0mol/L;
s2: when the reaction material reaches the target particle size, aging the reaction material, and carrying out solid-liquid separation to obtain the lithium cobaltate precursor;
tellurium is reduced into tellurium anions through thiosulfate to generate cobalt telluride, and a coprecipitate is formed with cobalt hydroxide, so that tellurium doping in the precursor is achieved; in the coprecipitation process, the reaction is always under the reducing atmosphere, and the oxidation of cobalt is avoided.
2. The method according to claim 1, wherein in step S1, the cobalt salt solution is at least one of a solution of cobalt sulfate, cobalt nitrate or cobalt chloride.
3. The method according to claim 1, wherein in step S1, the concentration of the cobalt salt solution is 1.0 to 2.0mol/L.
4. The method according to claim 1, wherein in step S1, the complexing agent is aqueous ammonia in an amount of 6.0 to 12.0 mol/L.
5. The method according to claim 1, wherein in step S1, the reaction temperature is controlled to 55-65 ℃, pH is controlled to 10-11, and ammonia concentration is controlled to 5-10g/L.
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| CN202210277546.6A CN114604904B (en) | 2022-03-21 | 2022-03-21 | Preparation method and application of tellurium-doped lithium cobalt oxide precursor |
| HU2400106A HUP2400106A1 (en) | 2022-03-21 | 2022-11-14 | Preparation method for and application of tellurium-doped lithium cobalt oxide precursor |
| GB2314106.2A GB2619454A (en) | 2022-03-21 | 2022-11-14 | Preparation method for and application of tellurium-doped lithium cobalt oxide precursor |
| DE112022002539.5T DE112022002539T5 (en) | 2022-03-21 | 2022-11-14 | Process for producing a tellurium-doped lithium cobaltate precursor and its use |
| PCT/CN2022/131586 WO2023179047A1 (en) | 2022-03-21 | 2022-11-14 | Preparation method for and application of tellurium-doped lithium cobalt oxide precursor |
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| CN108123114A (en) * | 2016-11-28 | 2018-06-05 | 华为技术有限公司 | Lithium cobaltate cathode material and preparation method thereof and lithium rechargeable battery |
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| CN108807928B (en) * | 2018-06-25 | 2021-04-20 | 宁德新能源科技有限公司 | Synthesis of metal oxide and lithium ion battery |
| CN114604904B (en) * | 2022-03-21 | 2023-06-13 | 广东邦普循环科技有限公司 | Preparation method and application of tellurium-doped lithium cobalt oxide precursor |
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