CN114709413A - Ternary material and application thereof - Google Patents
Ternary material and application thereof Download PDFInfo
- Publication number
- CN114709413A CN114709413A CN202210394676.8A CN202210394676A CN114709413A CN 114709413 A CN114709413 A CN 114709413A CN 202210394676 A CN202210394676 A CN 202210394676A CN 114709413 A CN114709413 A CN 114709413A
- Authority
- CN
- China
- Prior art keywords
- ternary material
- diffraction peak
- electrochemical device
- ratio
- ternary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 93
- 238000012360 testing method Methods 0.000 claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 5
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052759 nickel Inorganic materials 0.000 abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 abstract description 14
- 239000010941 cobalt Substances 0.000 abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000005245 sintering Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018416 Mn0.33O2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 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
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a ternary material and application thereof, wherein in an XRD result of a pole piece test, the intensity ratio of a 003 diffraction peak to a 104 diffraction peak of the ternary material is 0.8-1.0. In the ternary material, the ratio of the intensity of the 003 diffraction peak to the intensity of the 104 diffraction peak is in the range, so that the ternary material can exert the optimal electrochemical performance and is not influenced by the reduction of nickel and cobalt contents.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to a ternary material, and particularly relates to a ternary material and application thereof.
Background
Nickel-cobalt-manganese ternary layered material LiNixCoyMn1-x-yO2Is the first choice of a power battery system with high energy density. At present, commercial ternary material batteries generally have higher Co content (y is more than or equal to 0.15) and high nickel content (x is more than or equal to 0.8). Because Co is expensive and Co ore is scarce, the cost can be saved and the resources can be protected by reducing the cobalt content; secondly, high nickel materials have poor safety and low charging voltage, the utilization rate of reversible lithium is insufficient, and the safety and the service voltage of the materials can be improved by reducing the content of nickel.
However, the decrease of the Co content (y is less than or equal to 0.13) in the ternary material can reduce the overall conductivity of the material and improve the diffusion barrier of lithium ions in crystal lattices, thereby causing serious deterioration of the dynamic performance; the reduction of the content of Ni leads to the reduction of the reversible specific capacity of the material.
Based on the above research, it is necessary to provide a ternary material, which has a balance among lithiation degree, surface free lithium content, crystallinity and lithium-nickel mixed-row under the premise of low cost, and can exert the optimal electrochemical performance of the ternary material.
Disclosure of Invention
The invention aims to provide a ternary material and application thereof, and particularly relates to a low-nickel and low-cobalt ternary material and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a ternary material having an intensity ratio of the 003 diffraction peak to the 104 diffraction peak of 0.8 to 1.0 as a result of XRD performed on a pole piece test.
In the ternary material, the ratio of the 003 diffraction peak intensity to the 104 diffraction peak intensity is in the range, so that the lithiation degree, the surface free lithium content, the crystallinity and the lithium-nickel mixed-row of the ternary material can be balanced, the low-nickel and low-cobalt ternary material can exert the optimal electrochemical performance, and the ternary material is not influenced by the reduction of the nickel and cobalt contents; meanwhile, the ratio of the diffraction intensity and the nickel and cobalt with specific content are matched, so that low cost and high safety performance can be considered.
The intensity ratio of the 003 diffraction peak to the 104 diffraction peak refers to the integral intensity ratio of the corresponding diffraction peak.
The XRD of the ternary material has an intensity ratio of the 003 diffraction peak to the 104 diffraction peak of 0.8 to 1.0, which may be, for example, 0.8, 0.825, 0.85, 0.875, 0.9, 0.925, 0.95, 0.975 or 1.0, but is not limited to the values recited, and other values not recited in the numerical range may be used.
Preferably, the composition of the ternary material comprises LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.55 and less than or equal to 0.60, and y is more than or equal to 0.10 and less than or equal to 0.12.
The composition of the ternary material comprises LiNixCoyMn1-x-yO2Where 0.55. ltoreq. x.ltoreq.0.60 may be, for example, 0.55, 0.56, 0.57, 0.58, 0.59 or 0.60, but is not limited to the values listed, and other values not listed in the numerical range may also be suitable.
The composition of the ternary material comprises LiNixCoyMn1-x-yO2Where 0.10. ltoreq. y.ltoreq.0.12, for example 0.10, 0.105, 0.11, 0.115 or 0.12, but is not limited to the values listed, and other values not listed in the numerical range are also suitable.
Preferably, the composition of the ternary material further comprises residual lithium ions.
Preferably, the residual lithium ion content is from 300ppm to 800ppm, and may be, for example, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm or 800ppm, but is not limited to the recited values, and other values not recited within the numerical ranges are applicable.
The ternary material also comprises residual lithium ions, and the existence of the residual lithium ions in a reasonable content range can improve the ionic conductivity of the low-nickel and low-cobalt ternary material, and is favorable for the extraction and the insertion of the lithium ions.
Preferably, the residual lithium ionsWith the particle diameter D of the ternary material50The ratio of (B) is 150 ppm/. mu.m to 350 ppm/. mu.m, and may be, for example, 150 ppm/. mu.m, 175 ppm/. mu.m, 200 ppm/. mu.m, 225 ppm/. mu.m, 250 ppm/. mu.m, 275 ppm/. mu.m, 300 ppm/. mu.m, 325 ppm/. mu.m or 350 ppm/. mu.m, but is not limited to the values recited, and other values not recited in the numerical ranges may also be applicable.
The invention controls the content of residual lithium ions and the particle size D of the ternary material50The structural stability of the ternary material can be optimized.
Preferably, the molar ratio of lithium ions to other metal ions in the starting materials for the preparation of the ternary material is (1.05 to 1.09):1, and may be, for example, 1.05:1, 1.06:1, 1.07:1, 1.08:1 or 1.09:1, but is not limited to the recited values, and other values not recited in the numerical range may still be applicable.
In the raw materials for preparing the ternary material, the content of lithium ions is slightly excessive, so that the residual lithium content of the obtained low-nickel and low-cobalt ternary material is in a reasonable range, and the low-nickel and low-cobalt ternary material can exert the optimal electrochemical performance.
The preparation method of the ternary material comprises the following steps:
and mixing the ternary material precursor and lithium salt according to the formula amount, and sintering to obtain the ternary material.
Preferably, the sintering temperature is 930 ℃ to 980 ℃, for example 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃ or 980 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the sintering time is 14h to 22h, for example, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h or 22h, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In a second aspect, the present invention provides an electrochemical device comprising a ternary material as described in the first aspect.
Preferably, the composition of the positive electrode sheet of the electrochemical device includes the ternary material, the conductive agent and the binder in a mass ratio of (90 to 99): 0.1 to 7):1, and may be, for example, 90:0.1:1, 95:2:1, 97:6:1 or 99:7:1, but is not limited to the enumerated values, and other unrecited values within the numerical range may still be applicable.
Preferably, the composition of the negative electrode sheet of the electrochemical device includes (90 to 99): 0.1 to 5):2 graphite, a conductive agent and a binder, which may be, for example, 90:0.1:2, 95:3:2 or 99:5:2, but is not limited to the enumerated values, and other values within the numerical range that are not enumerated are still applicable.
Preferably, the electrolyte of the electrochemical device includes lithium hexafluorophosphate.
In a third aspect, the present invention provides an electronic device comprising an electrochemical apparatus according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the lithiation degree, the surface free lithium content, the crystallinity and the lithium-nickel mixed discharge of the ternary material are balanced by controlling the ratio of the diffraction peak intensities in the ternary material, so that the low-nickel and low-cobalt ternary material can have excellent electrochemical performance and is not influenced by the reduction of the nickel and cobalt contents on the material.
Drawings
Figure 1 is the XRD pattern of the ternary material described in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a ternary material having a composition comprising LiNi0.58Co0.11Mn0.31O2And further comprises 399ppm of residual lithium ions; the content of the residual lithium ions and the particle diameter D of the ternary material50The ratio of (A) to (B) is 230ppm/μm;
the XRD result of the ternary material in a pole piece test is shown in figure 1, and the intensity ratio of a 003 diffraction peak to a 104 diffraction peak is 0.85; wherein, the 2 theta corresponding to the 003 diffraction peak is 18.618 degrees, the half-peak width is 0.149, the 2 theta corresponding to the 104 diffraction peak is 44.301 degrees, and the half-peak width is 0.174;
in the preparation raw materials of the ternary material, the molar ratio of lithium ions to other metal ions is 1.07: 1;
the preparation method of the ternary material comprises the following steps:
and mixing the ternary material precursor and lithium carbonate according to the formula amount, and sintering at 950 ℃ for 18h to obtain the ternary material.
Example 2
This example provides a ternary material having a composition comprising LiNi0.55Co0.12Mn0.33O2And further comprising 300ppm residual lithium ions; the content of the residual lithium ions and the particle diameter D of the ternary material50The ratio of (A) to (B) is 150ppm/μm;
in an XRD result of a pole piece test of the ternary material, the ratio of the intensity of a 003 diffraction peak to the intensity of a 104 diffraction peak is 0.8;
in the preparation raw materials of the ternary material, the molar ratio of lithium ions to other metal ions is 1.05: 1;
the preparation method of the ternary material comprises the following steps:
and mixing the precursor of the ternary material and LiOH according to the formula amount, and sintering at 930 ℃ for 22h to obtain the ternary material.
Example 3
This example provides a ternary material having a composition comprising LiNi0.60Co0.10Mn0.30O2And also 800ppm of residual lithium ions; the content of the residual lithium ions and the particle diameter D of the ternary material50The ratio of (d) is 350 ppm/. mu.m.
In an XRD result of a pole piece test of the ternary material, the ratio of the intensity of a 003 diffraction peak to the intensity of a 104 diffraction peak is 1.0;
in the preparation raw materials of the ternary material, the molar ratio of lithium ions to other metal ions is 1.09: 1;
the preparation method of the ternary material comprises the following steps:
and mixing the ternary material precursor and lithium carbonate according to the formula amount, and sintering at 980 ℃ for 14h to obtain the ternary material.
Examples 4 to 6 provided ternary materials as shown in table 2, which were the same as in example 1 except that the content of residual lithium ions was changed, and the molar ratio of lithium ions to other metal ions in the preparation raw materials was changed.
Examples 7 to 8 provided ternary materials as shown in table 3, except for the content of the residual lithium ions and the particle diameter D of the ternary material50Change in the ratio of (A) to (B), particle size D of the corresponding ternary material50The procedure was as in example 1 except for the change.
The ternary materials provided in comparative examples 1 and 2 are the same as those of example 1 except that the intensity ratio of the 003 diffraction peak to the 104 diffraction peak is changed as shown in Table 4.
And (3) performance testing:
the ternary material obtained in the above examples and comparative examples, conductive carbon black, carbon nanotubes and polyvinylidene fluoride were mixed in a mass ratio of 97:1:0.5:1, and made into slurry in N-methylpyrrolidone solvent, and then coated on aluminum foil, dried, and rolled to obtain a positive electrode sheet; putting graphite, conductive carbon black, sodium carboxymethylcellulose and styrene butadiene rubber in a mass ratio of 96:0.5:0.5:2 in an N-methyl pyrrolidone solvent, coating the obtained slurry on a copper foil, drying and rolling to obtain a negative plate; and assembling the obtained positive plate, the polyethylene diaphragm and the lithium hexafluorophosphate electrolyte into the lithium ion battery.
In the anode plate obtained by disassembling the lithium ion battery, powder obtained by scraping is slowly swept for 2 degrees/min by an X-ray diffractometer (model: D8 Advance of Bruker), the diffraction peak intensities of 003 and 104 are measured, and the intensity ratio is calculated; the content of residual lithium ions in the ternary material can be measured by a titration method; the chemical formula and the grain diameter D of the ternary material can be respectively determined through elemental analysis and a scanning electron microscope50。
Gram volume test method: under the condition of 25 ℃, charging and discharging for one week in a charging and discharging mode of 0.063A/g, the cut-off voltage is 2.8-4.4V, and the obtained charging/discharging capacity is divided by the usage amount of the positive electrode, namely the first gram capacity of charging/discharging; the test equipment is a battery performance test system (equipment model: BTS05/10C8D-HP) of the Shenghong electric appliance GmbH.
Circulation capacity retention test method: the obtained lithium ion battery is cycled at 25 ℃ in a charging and discharging mode of 0.19A/g (calculated by the mass of the anode material), and after the cycle is up to 800 weeks, the discharge capacity of the battery at the moment is divided by the discharge capacity of the first cycle, so that the cycle capacity retention rate of the battery at 800 cycles is obtained; the test equipment is a battery performance test system (equipment model: BTS05/10C8D-HP) of the Shenghong electric appliance GmbH.
The test results are shown in the following table:
TABLE 1
| First discharge gram capacity (mAh/g) | Retention ratio of 800-week-cycle Capacity (%) | |
| Example 1 | 187 | 95 |
| Example 2 | 184 | 95 |
| Example 3 | 183 | 91 |
TABLE 2
TABLE 3
TABLE 4
From the above table it can be seen that:
as can be seen from examples 1 to 8 and comparative examples 1 to 2, the intensity ratio of the 003 diffraction peak to the 104 diffraction peak of the ternary material of the present invention is in the range of 0.8 to 1.0, and thus has excellent electrochemical properties; from examples 1 and 4 to 8, it can be seen that the residual lithium content and the residual lithium ion content in the ternary material and the particle diameter D of the material50The ratio of (a) to (b) all affect the electrochemical performance of the ternary material.
In conclusion, the invention provides the low-nickel and low-cobalt ternary material, which has lower nickel and cobalt contents, simultaneously has the electrochemical performance which is not influenced by the low nickel and cobalt contents, and has better electrochemical performance.
The above description is only for the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. A ternary material, wherein the ternary material has an intensity ratio of the 003 diffraction peak to the 104 diffraction peak of 0.8 to 1.0 as a result of XRD in a pole piece test.
2. The ternary material of claim 1, wherein the composition of the ternary material comprises LiNixCoyMn1-x-yO2And residual lithium ions, wherein x is more than or equal to 0.55 and less than or equal to 0.60, and y is more than or equal to 0.10 and less than or equal to 0.12.
3. The ternary material according to claim 2, characterized in that said residual lithium ion content is comprised between 300 and 800 ppm.
4. Ternary material according to claim 3, characterised in that the content of residual lithium ions and the particle size D of the ternary material50The ratio of (A) is 150ppm/μm to 350ppm/μm.
5. The ternary material according to claim 1, wherein the molar ratio of lithium ions to other metal ions in the starting materials for the preparation of said ternary material is (1.05 to 1.09): 1.
6. An electrochemical device comprising a ternary material according to any one of claims 1 to 5.
7. The electrochemical device according to claim 6, wherein the composition of the positive electrode sheet of the electrochemical device comprises the ternary material, the conductive agent and the binder in a mass ratio of (90 to 99): (0.1 to 7): 1.
8. The electrochemical device according to claim 6, wherein the negative electrode sheet of the electrochemical device has a composition comprising (90 to 99): 0.1 to 5):2 graphite, a conductive agent, and a binder.
9. The electrochemical device of claim 6, wherein the electrolyte of the electrochemical device comprises lithium hexafluorophosphate.
10. An electronic device, characterized in that it comprises an electrochemical device according to any one of claims 6 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210394676.8A CN114709413A (en) | 2022-04-14 | 2022-04-14 | Ternary material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210394676.8A CN114709413A (en) | 2022-04-14 | 2022-04-14 | Ternary material and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114709413A true CN114709413A (en) | 2022-07-05 |
Family
ID=82175218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210394676.8A Pending CN114709413A (en) | 2022-04-14 | 2022-04-14 | Ternary material and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114709413A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115548334A (en) * | 2022-12-01 | 2022-12-30 | 欣旺达电动汽车电池有限公司 | Positive active material and lithium ion battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102171863A (en) * | 2008-12-24 | 2011-08-31 | 日本碍子株式会社 | Plate-shaped particles for positive electrode active material of lithium secondary batteries, films of said material as well as lithium secondary batteries |
| JP2016110889A (en) * | 2014-12-09 | 2016-06-20 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | Positive electrode active material, and lithium ion secondary battery |
| CN105702952A (en) * | 2014-12-09 | 2016-06-22 | 三星Sdi株式会社 | Positive active material for rechargeable lithium battery and rechargeable lithium battery |
| WO2017150506A1 (en) * | 2016-02-29 | 2017-09-08 | 三井金属鉱業株式会社 | Positive electrode active material for lithium secondary battery |
| CN109360948A (en) * | 2018-09-11 | 2019-02-19 | 天津市捷威动力工业有限公司 | The nickelic multicomponent material presoma of one type monocrystalline type |
| CN109461926A (en) * | 2018-11-09 | 2019-03-12 | 烟台卓能锂电池有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof, anode and lithium ion battery |
| CN110214390A (en) * | 2017-03-06 | 2019-09-06 | 松下知识产权经营株式会社 | Positive active material and battery |
| CN114275830A (en) * | 2021-12-28 | 2022-04-05 | 深圳市贝特瑞纳米科技有限公司 | Low-cobalt ternary single crystal material, preparation method thereof and lithium ion battery anode material |
-
2022
- 2022-04-14 CN CN202210394676.8A patent/CN114709413A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102171863A (en) * | 2008-12-24 | 2011-08-31 | 日本碍子株式会社 | Plate-shaped particles for positive electrode active material of lithium secondary batteries, films of said material as well as lithium secondary batteries |
| JP2016110889A (en) * | 2014-12-09 | 2016-06-20 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | Positive electrode active material, and lithium ion secondary battery |
| CN105702952A (en) * | 2014-12-09 | 2016-06-22 | 三星Sdi株式会社 | Positive active material for rechargeable lithium battery and rechargeable lithium battery |
| WO2017150506A1 (en) * | 2016-02-29 | 2017-09-08 | 三井金属鉱業株式会社 | Positive electrode active material for lithium secondary battery |
| CN110214390A (en) * | 2017-03-06 | 2019-09-06 | 松下知识产权经营株式会社 | Positive active material and battery |
| CN109360948A (en) * | 2018-09-11 | 2019-02-19 | 天津市捷威动力工业有限公司 | The nickelic multicomponent material presoma of one type monocrystalline type |
| CN109461926A (en) * | 2018-11-09 | 2019-03-12 | 烟台卓能锂电池有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof, anode and lithium ion battery |
| CN114275830A (en) * | 2021-12-28 | 2022-04-05 | 深圳市贝特瑞纳米科技有限公司 | Low-cobalt ternary single crystal material, preparation method thereof and lithium ion battery anode material |
Non-Patent Citations (1)
| Title |
|---|
| 蔡国强等: ""三元材料表面残留锂对电池性能的影响"", 广东化工, vol. 41, no. 21, 30 November 2014 (2014-11-30), pages 133 - 134 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115548334A (en) * | 2022-12-01 | 2022-12-30 | 欣旺达电动汽车电池有限公司 | Positive active material and lithium ion battery |
| WO2024113430A1 (en) * | 2022-12-01 | 2024-06-06 | 欣旺达动力科技股份有限公司 | Positive electrode active material and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102738458B (en) | Surface modification method of lithium-rich cathode material | |
| US20180226639A1 (en) | Carbon-coated ternary positive electrode material, preparation method therefor, and lithium ion battery | |
| US20150118563A1 (en) | Lithium-rich positive electrode material, lithium battery positive electrode, and lithium battery | |
| KR20170075596A (en) | Positive electrode active material for rechargeable lithium battery, method for menufacturing the same, and rechargeable lithium battery including the same | |
| TWI725822B (en) | Lithium battery and anode material thereof | |
| CN111435742A (en) | Positive active material, positive pole piece and sodium ion battery | |
| CN108767226B (en) | Metal phthalocyanine compound coated ternary cathode material and preparation method thereof | |
| CN114094068B (en) | Cobalt-coated positive electrode material, preparation method thereof, positive electrode plate and lithium ion battery | |
| CN111009645A (en) | graphene-based/AlPO4Method for compositely coating modified high-nickel ternary cathode material | |
| JP2010272272A (en) | Positive electrode for lithium secondary battery, and lithium secondary battery | |
| CN114744186B (en) | Layered lithium-rich manganese-based composite positive electrode material, preparation method and battery | |
| CN113060775A (en) | Cobalt-free cathode material and preparation method and application thereof | |
| CN113782735A (en) | Sodium ion battery positive electrode material, sodium ion battery, preparation method and electric equipment | |
| CN108682828B (en) | Preparation method of nitrogen-doped carbon-coated positive electrode material | |
| CN113173606B (en) | Modification method for improving performance of lithium-rich iron-manganese-based cathode material based on density functional theory calculation | |
| WO2024103956A1 (en) | Positive electrode material, and positive electrode sheet and battery comprising same | |
| CN113644274A (en) | O2 type lithium ion battery anode material and preparation method and application thereof | |
| CN113921792A (en) | Lithium ion battery positive pole piece and preparation method and application thereof | |
| CN114709413A (en) | Ternary material and application thereof | |
| WO2014071724A1 (en) | Lithium-rich anode material, lithium battery anode, and lithium battery | |
| CN109216692B (en) | Modified ternary cathode material, preparation method thereof and lithium ion battery | |
| CN116805684A (en) | Al, zn, ti and Fe co-doped biphase layered oxide sodium ion battery high-entropy positive electrode material | |
| CN116111083A (en) | Positive electrode material, positive electrode sheet and sodium ion battery | |
| Sun et al. | Preparation of CeO2-coated Li1. 2Mn0. 54Co0. 13Ni0. 13O2 as cathode materials for Lithium Ion Batteries | |
| Feng et al. | Effect of calcination time on lithium ion diffusion coefficient of LiMg0. 04Mn1. 96O4 prepared by a solid-state combustion method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |