CN108878807A - High Ni-based quaternary positive electrode and preparation method thereof - Google Patents
High Ni-based quaternary positive electrode and preparation method thereof Download PDFInfo
- Publication number
- CN108878807A CN108878807A CN201810564989.7A CN201810564989A CN108878807A CN 108878807 A CN108878807 A CN 108878807A CN 201810564989 A CN201810564989 A CN 201810564989A CN 108878807 A CN108878807 A CN 108878807A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- sintering
- based quaternary
- preparation
- quaternary positive
- 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
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
- H01M4/362—Composites
-
- 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
-
- 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
Abstract
Present invention discloses a kind of high Ni-based quaternary positive electrode and preparation method thereof, the positive electrode molecular formula is LiNix Coy Nz Mn(1‑x‑y‑z)O2, the N is at least one of Al, Ti, Zr, wherein and 80% < x < 94%, 5%<y<15%, 1%≤z<5%, 1-x-y-z ≠ 0；The preparation method includes precursor material being added to the water, and mixed base is added and is adjusted to specified PH, at room temperature it is coprecipitated it is fixed after, through obtaining presoma in specified drying process；The presoma and pre-composition solid phase are sufficiently mixed, first sintering is carried out, once sintered product is obtained after sintering；The once sintered product carries out second and is sintered, and obtains double sintering product；The double sintering product obtains the Ni-based quaternary positive electrode of the height by sieving, removing impurity.
Description
Technical field
The present invention relates to positive electrode field, a kind of high Ni-based quaternary positive electrode and its preparation side are especially related to
Method.
Background technique
The promotion of power battery core energy density is to promote electric vehicle course continuation mileage key technology bottleneck；However, in battery core just
The energy density of pole material largely determines the energy density of power battery core.
Currently, stratiform nickel-cobalt-manganese ternary material is the most important positive electrode of current driving force battery core, improve in ternary material
Nickel content, can effectively improve ternary material gram volume performance.But it can bring that surface alkalinty is bigger than normal, crystalline surface oxygen is steady simultaneously
Qualitative more low counter productive, eventually lead under its high temperature produce gas it is larger, storage performance is poor.
Currently, nickelic improve the mode for producing gas, mainly during the sintering process, micro (ppm grades) additive is added, improve body
Phase lattice stability.Meanwhile using the post-processing such as washing and cladding after sintering, interface stability is promoted.The prior art is original
It is finely adjusted in material, is optimized mainly for material surface, the retention time is shorter, and surface is easily destroyed；Surface treatment
Technique is relatively more complicated, increases positive electrode synthesis procedure and synthesis cost.
Summary of the invention
The main object of the present invention is to provide that a kind of storage performance is good, high temperature produce the low Ni-based quaternary positive electrode of height of gas and
Preparation method.
For achieving the above object, the present invention proposes a kind of high Ni-based quaternary positive electrode, and positive electrode molecular formula is
LiNixCoyNzMn(1-x-y-z)O2, at least one of N Al, Ti, Zr, wherein and 80% < x < 94%, 5%<y<15%, 1%≤
z<5%, 1-x-y-z ≠ 0.
The present invention also proposes a kind of preparation method of high Ni-based quaternary positive electrode, including,
Precursor material is added to the water, and mixed base is added and is adjusted to specified pH, when coprecipitated surely specified at room temperature
Between after, under an inert atmosphere, designated drying process obtains presoma.
After the presoma and pre-composition solid phase are sufficiently mixed, the is carried out in the first sintering temperature, the first sintering time
After once sintered, designated processing technology obtains once sintered product.
After the once sintered product is mixed with additive, carried out in the second sintering temperature, the second sintering time secondary
After sintering, designated aftertreatment technology obtains the Ni-based quaternary positive electrode of the height.
Further, the presoma includes nickel salt, cobalt salt and manganese salt, and the pre-composition includes at least one in Al, Ti, Zr
The compound and lithium salts of kind element；The precursor molecule formula is NixCoyMn(1-x-y-z)(OH)2。
Further, the precursor material includes the change of at least one of nickel salt, cobalt salt, manganese salt and Al, Ti, Zr element
Object is closed, the pre-composition includes lithium salts, and the precursor molecule formula is NixCoyNzMn(1-x-y-z)(OH)2。
Further, the nickel salt includes nickel sulfate or nickel nitrate；The cobalt salt includes cobaltous sulfate or cobalt nitrate；The manganese
Salt includes manganese sulfate or manganese nitrate；The lithium salts includes lithium carbonate or lithium hydroxide；At least one of described Al, Ti, Zr element
Compound include aluminium oxide, it is aluminium hydroxide, titanium oxide, titanium hydroxide, zirconium oxide, one or more of in zirconium hydroxide.
Further, the nickel element in the nickel salt：Cobalt element in cobalt salt：Manganese element in manganese salt：In Al, Ti, Zr
At least one element：The mass ratio of the material of elemental lithium is x in lithium salts：y：(1-x-y-z)：z：(1~1.1), wherein 80% < x
< 94%, 5%<y<15%, 1%≤z<5%, 1-x-y-z ≠ 0.
Further, the specified PH includes 10~11；The specified time includes 8~12h；First sintering temperature
Including 700~800 DEG C；First sintering time includes 8~12h；Second sintering temperature includes 300~600 DEG C；It is described
Second sintering time includes 6~8h.
Further, the mixed base includes ammonium hydroxide and NaOH aqueous solution；The ammonia concn is 0.5-5mol/L, described
NaOH concentration of aqueous solution is 3-5mol/L, and the volume ratio of the ammonium hydroxide and NaOH aqueous solution is (5~20):1.
Further, the inert atmosphere includes nitrogen atmosphere.
Further, the additive includes Al2O3、AlCl3、SrCl2、TiO2、MgO、CaO、SiO2、ZnO、Nb2O5、
V2O5、B2O3Middle one or more.
High Ni-based quaternary positive electrode of the invention and preparation method thereof is compared with the prior art, and beneficial effect is in ternary
In material matrix, a large amount of doping introduce Al, Ti, Zr element (1-5%, 10000-50000ppm), stronger with Ti, Zr using Al
With oxygen key and ability and electrochemical stability, stabilizing material base structure itself.Meanwhile Ni content and Co content are properly increased,
Guarantee that gram volume plays.Using the characteristic of each element in Ni, Co, Mn, N (N=Al, Ti, Zr) quaternary matrix, guaranteeing energy
In the case where density, there is lower high temperature gas production and better storage performance.
Detailed description of the invention
The flow diagram of the preparation method of the high Ni-based quaternary positive electrode of Fig. 1 one embodiment of the invention；
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
A kind of high Ni-based quaternary positive electrode, molecular formula LiNix Coy Nz Mn(1-x-y-z)O2, in N Al, Ti, Zr extremely
Few one kind, wherein 80% < x < 94%, 5%<y<15%, 1%≤z<5%, 1-x-y-z ≠ 0.
Referring to Fig.1, the preparation method of the Ni-based quaternary positive electrode of height of one embodiment of the invention, including,
S1：Precursor material is added to the water, and mixed base is added and is adjusted to specified PH, it is coprecipitated fixed specified at room temperature
After time, under an inert atmosphere, designated drying process obtains presoma.
In one embodiment of the invention, precursor material includes nickel salt, cobalt salt, manganese salt；The precursor molecule formula
For NixCoyMn(1-x-y-z)(OH)2。
In one embodiment of the invention, precursor material includes nickel salt, cobalt salt, at least one in manganese salt and Al, Ti, Zr
The compound of kind element；The precursor molecule formula is NixCoyNzMn(1-x-y-z)(OH)2。
Nickel salt includes nickel sulfate or nickel nitrate, and cobalt salt includes cobaltous sulfate or cobalt nitrate, and manganese salt includes manganese sulfate or manganese nitrate,
The compound of at least one of Al, Ti, Zr element includes aluminium hydroxide, aluminium oxide, titanium hydroxide, titanium oxide, zirconium hydroxide, oxygen
Change one or more of in zirconium；Nickel element in nickel salt：Cobalt element in cobalt salt：Manganese element in manganese salt：In Al, Ti, Zr at least
A kind of the mass ratio of the material of element is x：y：(1-x-y-z)：z；Mixed base includes ammonium hydroxide and NaOH aqueous solution, and ammonia concn includes
0.5mol/L to 5mol/L, NaOH concentration of aqueous solution include 3mol/L to 5mol/L, and the volume ratio of ammonium hydroxide and NaOH aqueous solution is
(5~20):1；Specified PH includes 10~11；Specified time includes 8~12h；Inert atmosphere includes nitrogen atmosphere；Specified back tender
Skill includes：Drying time is 4 to 6h, and drying temperature is 100 DEG C to 120 DEG C.
This step is by co-precipitation, so that the ratio of precursor material refinement and precursor material each component is more constant,
This process is simple, preparation condition is easily controllable, synthesis cycle is short simultaneously.Logical nitrogen is in order to prevent in presoma when dry
The oxidation of main material metal, the final performance for influencing positive electrode.
S2：After the presoma and pre-composition solid phase are sufficiently mixed, carried out in the first sintering temperature, the first sintering time
After first sintering, designated processing technology obtains once sintered product.
In one embodiment of the invention, pre-composition includes the compound and lithium of at least one of Al, Ti, Zr element
Salt.
In one embodiment of the invention, pre-composition includes lithium salts.
The compound of at least one of Al, Ti, Zr element includes aluminium hydroxide, aluminium oxide, titanium hydroxide, titanium oxide, hydrogen
One or more of in zirconium oxide, zirconium oxide, lithium salts includes lithium carbonate or lithium hydroxide, at least one of Al, Ti, Zr element：Lithium
The mass ratio of the material of elemental lithium is z in salt：(1~1.1)；First sintering temperature includes 700~800 DEG C；First sintering time packet
Include 8~12h；The processing technology be included in crusher carry out crush sieved in electromagnet vibrating screen.
This step keeps solid particle mutually bonded by high temperature sintering, and crystal grain is grown up, and stomata and crystal boundary are reduced, and density increases
Add, enhances chemical property；Meanwhile high temperature sintering aoxidizes the metal impurities in material, removes using crushing and sieving
Impurity improves the safety of positive electrode.
S3：After the once sintered product is mixed with additive, two are carried out in the second sintering temperature, the second sintering time
After secondary sintering, designated aftertreatment technology obtains the Ni-based quaternary positive electrode of the height.
In above-mentioned steps, additive includes Al2O3、AlCl3、SrCl2、TiO2、MgO、CaO、SiO2、ZnO、Nb2O5、
V2O5、B2O3Middle one or more；Second sintering temperature includes 300~600 DEG C；Second sintering time includes 6~8h；Post-processing
Technique is included in crusher and is crushed, and powder is sieved with electromagnet vibrating screen by the permanent magnet in powder transfer pipeline
Mode removes magnetisable material in material to obtain high Ni-based quaternary positive electrode LiNix Coy Nz Mn(1-x-y-z)O2。
This step repairs lattice defect by low-temperature sintering, improves crystallinity, so that positive electrode lattice is fine and close, improves
Body phase lattice stability；Double sintering makes material reaction sufficiently simultaneously, reduces specific surface area and mentions so that particle distribution is uniform
High electrode capacity；Additive is cladding metallic element compound, can effectively improve body phase lattice stability；Remove the magnetic in material
Property impurity improve positive electrode safety；.
The preparation process of the Ni-based quaternary positive electrode of height of the present embodiment includes：
By the nickel element in nickel salt：Cobalt element in cobalt salt：Manganese element in manganese salt：At least one of Al, Ti, Zr element
Al, Ti, Zr element of compound：The mass ratio of the material of elemental lithium is x in lithium salts：y：(1-x-y-z)：z：The material of (1~1.1)
It is ready to；Precursor material is added to the water, and it includes 0.5mol/L dense to 5mol/L, NaOH aqueous solution that ammonia concn, which is added,
Spending includes 3mol/L to 5mol/L, and the volume ratio of ammonium hydroxide and NaOH aqueous solution is 5:1 to 20:1 mixed base, adjusting PH to 10~
11, it at room temperature after coprecipitated fixed 8~12h, dries in a nitrogen atmosphere, drying temperature is 100 DEG C to 120 DEG C, drying time 4
To 6h, presoma is obtained；It include 700~800 DEG C, sintering time in sintering temperature after presoma and pre-composition are sufficiently mixed
After carrying out first sintering including 8~12h, crush in crusher and once be burnt with being sieved in electromagnet vibrating screen
Tie product；By the once sintered product and additive be blended in sintering temperature include 300~600 DEG C, sintering time include 6~
After 8h carries out double sintering, after crusher is crushed, pass through the permanent magnet and electromagnet vibrating screen in powder transfer pipeline
The mode that powder is sieved, magnetisable material in material is removed, the Ni-based quaternary positive electrode LiNi of the height is obtainedx Coy Nz
Mn(1-x-y-z)O2。
Embodiment 1
By nickel sulfate：Cobaltous sulfate：Manganese sulfate：Titanium dioxide：The mass ratio of the material value of the metallic element of lithium hydroxide is
0.803：0.014：0.012：0.045：1 material is got ready, nickel sulfate, cobaltous sulfate, manganese sulfate is added to the water, and ammonia is added
It is 5mol/L that water concentration, which is 0.5mol/L, NaOH concentration of aqueous solution, and the volume ratio of ammonium hydroxide and NaOH aqueous solution is 20:1 mixing
Alkali, adjust PH to 10~11, at room temperature it is coprecipitated determine 10h after, dry in a nitrogen atmosphere, drying temperature be 100 DEG C, dry when
Between be 6h, obtain presoma；After presoma and aluminium hydroxide, lithium hydroxide are sufficiently mixed, it is 700 DEG C, burns in sintering temperature
Tying the time is crush in crusher and be sieved in electromagnet vibrating screen, obtained primary after 12h carries out first sintering
Sintered product；By the once sintered product and Al2O3Mixing, sintering temperature be 300 DEG C, sintering time include 8h carry out two
After secondary sintering, after crusher is crushed, by permanent magnet in powder transfer pipeline and electromagnet vibrating screen by powder mistake
The mode of sieve removes magnetisable material in material, obtains high Ni-based quaternary positive electrode A.
Embodiment 2
By nickel nitrate：Cobalt nitrate：Manganese nitrate：Zirconium oxide：The mass ratio of the material value of the metallic element of lithium carbonate is 0.84：
0.12：0.03：0.01：1.02 material is ready to, and nickel nitrate, cobalt nitrate, manganese nitrate, zirconium oxide are added to the water, and is added
It is 4mol/L that enter ammonia concn, which be 3mol/L, NaOH concentration of aqueous solution, and the volume ratio of ammonium hydroxide and NaOH aqueous solution is 10:1 it is mixed
Close alkali, adjust PH to 10~11, at room temperature it is coprecipitated determine 9h after, dry in a nitrogen atmosphere, drying temperature be 110 DEG C, dry
Time is 5h, obtains presoma；After presoma and lithium carbonate are sufficiently mixed, sintering temperature is 750 DEG C, sintering time is
After 10h carries out first sintering, crush in crusher and be sieved in electromagnet vibrating screen, obtain once sintered production
Object；
By the once sintered product and TiO2Mixing, sintering temperature be 450 DEG C, sintering time include 7h carry out it is secondary
After sintering, after crusher is crushed, powder is sieved with electromagnet vibrating screen by the permanent magnet in powder transfer pipeline
Mode, magnetisable material in material is removed, high Ni-based quaternary positive electrode B is obtained.
Embodiment 3
By nickel sulfate：Cobaltous sulfate：Manganese sulfate：Aluminium hydroxide：The mass ratio of the material value of the metallic element of lithium hydroxide is
0.86：0.08：0.04：0.02：1.04 material is ready to, and nickel sulfate, cobaltous sulfate, manganese sulfate are added to the water, and is added
It is 4mol/L that ammonia concn, which is 2mol/L, NaOH concentration of aqueous solution, and the volume ratio of ammonium hydroxide and NaOH aqueous solution is 15:1 mixing
Alkali, adjust PH to 10~11, at room temperature it is coprecipitated determine 10h after, dry in a nitrogen atmosphere, drying temperature be 115 DEG C, dry when
Between be 4.5h, obtain presoma；After presoma and aluminium hydroxide, lithium hydroxide are sufficiently mixed, sintering temperature be 780 DEG C,
Sintering time is crush in crusher and be sieved in electromagnet vibrating screen, obtain one after 9h carries out first sintering
Secondary sintered product；The once sintered product is mixed with CaO, sintering temperature be 500 DEG C, sintering time include 6.5h carry out
After double sintering, after crusher is crushed, by permanent magnet in powder transfer pipeline and electromagnet vibrating screen by powder
The mode of sieving removes magnetisable material in material, obtains high Ni-based quaternary positive electrode C.
Embodiment 4
By nickel nitrate：Cobalt nitrate：Manganese nitrate：Titanium hydroxide：The mass ratio of the material value of the metallic element of lithium hydroxide is
0.88：0.01：0.01：0.1：1.06 material is ready to, and nickel nitrate, cobalt nitrate, manganese nitrate, titanium hydroxide are added to water
In, and it is 4mol/L that ammonia concn is added, which is 4mol/L, NaOH concentration of aqueous solution, the volume ratio of ammonium hydroxide and NaOH aqueous solution is 8:
1 mixed base, adjust PH to 10~11, at room temperature it is coprecipitated determine 8h after, dry in a nitrogen atmosphere, drying temperature be 105 DEG C,
Drying time is 5.5h, obtains presoma；After presoma and lithium hydroxide are sufficiently mixed, it is 730 DEG C, is sintered in sintering temperature
Time is crush in crusher and be sieved in electromagnet vibrating screen, once burnt after 11h carries out first sintering
Tie product；The once sintered product is mixed with MgO, sintering temperature be 400 DEG C, sintering time include 7.5h carry out it is secondary
After sintering, after crusher is crushed, powder is sieved with electromagnet vibrating screen by the permanent magnet in powder transfer pipeline
Mode, magnetisable material in material is removed, high Ni-based quaternary positive electrode D is obtained.
Embodiment 5
By nickel nitrate：Cobalt nitrate：Manganese nitrate：Zirconium hydroxide：The mass ratio of the material value of the metallic element of lithium carbonate is 0.9：
0.06：0.02：0.02：1.08 material is ready to, and nickel nitrate, cobalt nitrate, manganese nitrate is added to the water, and it is dense that ammonium hydroxide is added
It is 4mol/L that degree, which be 1mol/L, NaOH concentration of aqueous solution, and the volume ratio of ammonium hydroxide and NaOH aqueous solution is 12:1 mixed base is adjusted
PH to 10~11, at room temperature it is coprecipitated determine 11h after, dry in a nitrogen atmosphere, drying temperature be 110 DEG C, drying time 5h,
Obtain presoma；After presoma and titanium hydroxide, lithium carbonate are sufficiently mixed, sintering temperature is 750 DEG C, sintering time is
After 10h carries out first sintering, crush in crusher and be sieved in electromagnet vibrating screen, obtain once sintered production
Object；After the once sintered product is mixed with MgO, sintering temperature be 450 DEG C, sintering time include 7h carry out double sintering
Afterwards, it is crushed in crusher, in such a way that powder is sieved by the permanent magnet in powder transfer pipeline with electromagnet vibrating screen,
Magnetisable material in material is removed, high Ni-based quaternary positive electrode E is obtained.
Embodiment 6
By nickel sulfate：Cobaltous sulfate：Manganese sulfate：Aluminium oxide：The mass ratio of the material value of the metallic element of lithium carbonate is 0.933：
0.055：0.01：0.002：1.1 material is ready to, and nickel sulfate, cobaltous sulfate, manganese sulfate, aluminium oxide are added to the water, and is added
It is 3mol/L that enter ammonia concn, which be 5mol/L, NaOH concentration of aqueous solution, and the volume ratio of ammonium hydroxide and NaOH aqueous solution is 5:1 mixing
Alkali, adjust PH to 10~11, at room temperature it is coprecipitated determine 12h after, dry in a nitrogen atmosphere, drying temperature be 120 DEG C, dry when
Between be 4h, obtain presoma；After presoma and lithium carbonate are sufficiently mixed, sintering temperature be 800 DEG C, sintering time be 8h into
After row first sintering, crush in crusher and be sieved in electromagnet vibrating screen, obtain once sintered product；By institute
State once sintered product and B2O3After mixing, sintering temperature is 600 DEG C, sintering time includes after 6h carries out double sintering, broken
Broken machine is crushed, in such a way that powder is sieved by the permanent magnet in powder transfer pipeline with electromagnet vibrating screen, by material
Middle magnetisable material removes, and obtains high Ni-based quaternary positive electrode F.
Comparative example 1
It is added without the compound of at least one of Al, Ti, Zr element, nickel sulfate：Cobaltous sulfate：Manganese sulfate：Lithium hydroxide
The mass ratio of the material value of metallic element is 0.86：0.08：0.06：1.04, remaining is the same as embodiment 3.
The Ni-based quaternary positive electrode of height of Examples 1 to 6 provided by the invention and the Ni-based tertiary cathode material of height of comparative example 1
Material, positive electrode gram volume is tested under 4.2V voltage：
1 positive electrode gram volume test data of table
| 0.1C | 0.33C | 0.5C | 1C | |
| Embodiment 1 | 197.9mAh/g | 196mAh/g | 192mAh/g | 188mAh/g |
| Embodiment 2 | 203mAh/g | 201mAh/g | 197mAh/g | 194mAh/g |
| Embodiment 3 | 205mAh/g | 203mAh/g | 198mAh/g | 195mAh/g |
| Embodiment 4 | 207mAh/g | 205mAh/g | 201mAh/g | 196.8mAh/g |
| Embodiment 5 | 210.1mAh/g | 208mAh/g | 203.7mAh/g | 200mAh/g |
| Embodiment 6 | 212.1mAh/g | 210mAh/g | 205.5mAh/g | 202mAh/g |
| Comparative example 1 | 204mAh/g | 200mAh/g | 196mAh/g | 194mAh/g |
From can be higher with nickel content in positive electrode in table 1, gram volume be bigger；Embodiment 3 and the gram volume of comparative example 1 are poor
It is different little.
The Ni-based quaternary positive electrode of height of Examples 1 to 6 provided by the invention and the Ni-based tertiary cathode material of height of comparative example 1
Material, 80 DEG C of factor of created gase tests of positive electrode：
Table 2 positive electrode, 80 DEG C of factor of created gase data
| 0 day | 2 days | 4 days | 6 days | 8 days | 10 days | |
| Embodiment 1 | 0 | 7.5% | 14.0% | 19.0% | 24.0% | 30.0% |
| Embodiment 2 | 0 | 12.0% | 17.0% | 22.3% | 29.6% | 32.0% |
| Embodiment 3 | 0 | 14.0% | 17.5% | 22.0% | 28.7% | 32.7% |
| Embodiment 4 | 0 | 16.7% | 23.0% | 28.7% | 35.2% | 42.0% |
| Embodiment 5 | 0 | 18.0% | 24.0% | 29.0% | 34.0% | 40.0% |
| Embodiment 6 | 0 | 21.0% | 29.0% | 37.0% | 46.0% | 56.0% |
| Comparative example 1 | 0 | 36.0% | 40.0% | 60.4% | 72.0% | 88.0% |
The Ni-based quaternary positive electrode of height of Examples 1 to 6 is obviously higher by Ni-based three than comparative example 1 as can be seen from Table 2
The factor of created gase of first positive electrode is low, wherein embodiment 3 is identical as the content of nickel element and cobalt element in comparative example 1, embodiment
3 high temperature gas production about half lower than the high temperature gas production of comparative example 1.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all utilizations
Equivalent structure or equivalent flow shift made by description of the invention and accompanying drawing content is applied directly or indirectly in other correlations
Technical field, be included within the scope of the present invention.
Claims (10)
1. a kind of high Ni-based quaternary positive electrode, which is characterized in that the positive electrode molecular formula is LiNixCoyNzMn(1-x-y-z)
O2, the N is at least one of Al, Ti, Zr, wherein and 80% < x < 94%, 5%<y<15%, 1%≤z<5%, 1-x-y-z
≠0。
2. a kind of preparation method of the Ni-based quaternary positive electrode of height described in claim 1, which is characterized in that including,
Precursor material is added to the water, and mixed base is added and is adjusted to specified PH, at room temperature it is coprecipitated determine specified time after,
Under an inert atmosphere, designated drying process obtains presoma；
After the presoma and pre-composition solid phase are sufficiently mixed, carried out for the first time in the first sintering temperature, the first sintering time
After sintering, designated processing technology obtains once sintered product；
After the once sintered product is mixed with additive, double sintering is carried out in the second sintering temperature, the second sintering time
Afterwards, designated aftertreatment technology obtains the Ni-based quaternary positive electrode of the height.
3. the preparation method of high Ni-based quaternary positive electrode according to claim 2, which is characterized in that the presoma includes
Nickel salt, cobalt salt and manganese salt, the pre-composition include the compound and lithium salts of at least one of Al, Ti, Zr element；The presoma
Molecular formula is NixCoyMn(1-x-y-z)(OH)2。
4. the preparation method of high Ni-based quaternary positive electrode according to claim 2, which is characterized in that the precursor material
Compound including at least one of nickel salt, cobalt salt, manganese salt and Al, Ti, Zr element, the pre-composition includes lithium salts, before described
Drive body molecular formula is NixCoyNzMn(1-x-y-z)(OH)2。
5. according to the preparation method of the Ni-based quaternary positive electrode of the height of claim 3 or 4, which is characterized in that
The nickel salt includes nickel sulfate or nickel nitrate；
The cobalt salt includes cobaltous sulfate or cobalt nitrate；
The manganese salt includes manganese sulfate or manganese nitrate；
The lithium salts includes lithium carbonate or lithium hydroxide；
The compound of at least one of described Al, Ti, Zr element includes aluminium oxide, aluminium hydroxide, titanium oxide, titanium hydroxide, oxygen
Change one or more of zirconium, zirconium hydroxide.
6. according to the preparation method of the Ni-based quaternary positive electrode of the height of claim 3 or 4, which is characterized in that in the nickel salt
Nickel element：Cobalt element in cobalt salt：Manganese element in manganese salt：At least one of Al, Ti, Zr element：Elemental lithium in lithium salts
The mass ratio of the material is x：y：(1-x-y-z)：z：(1~1.1), wherein 80% < x < 94%, 5%<y<15%, 1%≤z<
5%, 1-x-y-z ≠ 0.
7. the preparation method of high Ni-based quaternary positive electrode according to claim 2, which is characterized in that
The specified PH includes 10~11；
The specified time includes 8~12h；
First sintering temperature includes 700~800 DEG C；
First sintering time includes 8~12h；
Second sintering temperature includes 300~600 DEG C；
Second sintering time includes 6~8h.
8. the preparation method of high Ni-based quaternary positive electrode according to claim 2, which is characterized in that the mixed base includes
Ammonium hydroxide and NaOH aqueous solution；The ammonia concn includes 0.5-5mol/L, and the NaOH concentration of aqueous solution includes 3-5mol/L, institute
The volume ratio for stating ammonium hydroxide and NaOH aqueous solution includes (5~20):1.
9. the preparation method of high Ni-based quaternary positive electrode according to claim 2, which is characterized in that the inert atmosphere packet
Include nitrogen atmosphere.
10. the preparation method of high Ni-based quaternary positive electrode according to claim 2, which is characterized in that the additive packet
Include Al2O3、AlCl3、SrCl2、TiO2、MgO、CaO、SiO2、ZnO、Nb2O5、V2O5、B2O3One or more of Deng.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810564989.7A CN108878807A (en) | 2018-06-04 | 2018-06-04 | High Ni-based quaternary positive electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810564989.7A CN108878807A (en) | 2018-06-04 | 2018-06-04 | High Ni-based quaternary positive electrode and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108878807A true CN108878807A (en) | 2018-11-23 |
Family
ID=64335265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810564989.7A Pending CN108878807A (en) | 2018-06-04 | 2018-06-04 | High Ni-based quaternary positive electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108878807A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244464A (en) * | 2020-02-16 | 2020-06-05 | 四川新锂想能源科技有限责任公司 | Zr and Al co-doped NCM ternary cathode material and preparation method thereof |
| CN111422919A (en) * | 2019-12-19 | 2020-07-17 | 蜂巢能源科技有限公司 | Quaternary positive electrode material, preparation method thereof, positive electrode and battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7314684B2 (en) * | 2003-03-14 | 2008-01-01 | U Chicago Argonne Llc | Layer cathode methods of manufacturing and materials for Li-ion rechargeable batteries |
| CN201308893Y (en) * | 2008-10-28 | 2009-09-16 | 天津巴莫科技股份有限公司 | Magnetic iron-removal vibration sieve |
| CN103490051A (en) * | 2013-09-18 | 2014-01-01 | 成都晶元新材料技术有限公司 | Multi-element anode lithium battery material suitable for high voltage and preparation method for material |
| CN103500827A (en) * | 2013-10-11 | 2014-01-08 | 宁德新能源科技有限公司 | Lithium ion battery and multi-element positive material thereof as well as preparation method of multi-element positive material |
| CN105453312A (en) * | 2013-07-24 | 2016-03-30 | 住友金属矿山株式会社 | Non-aqueous electrolyte secondary battery positive electrode active material and method for manufacturing same, and non-aqueous electrolyte secondary battery |
| CN107180950A (en) * | 2017-04-17 | 2017-09-19 | 张保平 | A kind of ternary cathode material of lithium ion battery NCM, NCA spray drying process preparation method |
| CN107516731A (en) * | 2017-07-18 | 2017-12-26 | 南京创源天地动力科技有限公司 | Modification lithium-ion battery anode material and preparation method thereof and the electrochemical energy storage device using modification lithium-ion battery anode material |
| CN107994212A (en) * | 2017-10-27 | 2018-05-04 | 合肥国轩高科动力能源有限公司 | A kind of layered cathode material of lithium ion battery and preparation method thereof |
-
2018
- 2018-06-04 CN CN201810564989.7A patent/CN108878807A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7314684B2 (en) * | 2003-03-14 | 2008-01-01 | U Chicago Argonne Llc | Layer cathode methods of manufacturing and materials for Li-ion rechargeable batteries |
| CN201308893Y (en) * | 2008-10-28 | 2009-09-16 | 天津巴莫科技股份有限公司 | Magnetic iron-removal vibration sieve |
| CN105453312A (en) * | 2013-07-24 | 2016-03-30 | 住友金属矿山株式会社 | Non-aqueous electrolyte secondary battery positive electrode active material and method for manufacturing same, and non-aqueous electrolyte secondary battery |
| CN103490051A (en) * | 2013-09-18 | 2014-01-01 | 成都晶元新材料技术有限公司 | Multi-element anode lithium battery material suitable for high voltage and preparation method for material |
| CN103500827A (en) * | 2013-10-11 | 2014-01-08 | 宁德新能源科技有限公司 | Lithium ion battery and multi-element positive material thereof as well as preparation method of multi-element positive material |
| CN107180950A (en) * | 2017-04-17 | 2017-09-19 | 张保平 | A kind of ternary cathode material of lithium ion battery NCM, NCA spray drying process preparation method |
| CN107516731A (en) * | 2017-07-18 | 2017-12-26 | 南京创源天地动力科技有限公司 | Modification lithium-ion battery anode material and preparation method thereof and the electrochemical energy storage device using modification lithium-ion battery anode material |
| CN107994212A (en) * | 2017-10-27 | 2018-05-04 | 合肥国轩高科动力能源有限公司 | A kind of layered cathode material of lithium ion battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111422919A (en) * | 2019-12-19 | 2020-07-17 | 蜂巢能源科技有限公司 | Quaternary positive electrode material, preparation method thereof, positive electrode and battery |
| CN111244464A (en) * | 2020-02-16 | 2020-06-05 | 四川新锂想能源科技有限责任公司 | Zr and Al co-doped NCM ternary cathode material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109461925A (en) | A kind of monocrystalline nickel-cobalt lithium manganate cathode material, presoma and preparation method thereof | |
| CN101621125B (en) | Nickel-cobalt-manganese multi-doped lithium ion battery cathode material and preparation method thereof | |
| CN103490051B (en) | One is applicable to high-tension multielement cathode lithium electric material and preparation method thereof | |
| CN102315429B (en) | The preparation method of aluminum-doped material of cathode of lithium ion battery with solid phase process | |
| CN104362295B (en) | A kind of lithium ion battery nickel-base anode material and preparation method thereof | |
| CN106505193A (en) | Monocrystalline nickel-cobalt lithium manganate cathode material and preparation method thereof and lithium ion battery | |
| CN108557905A (en) | A kind of lithium-rich manganese base material presoma and preparation method thereof, lithium-rich manganese-based anode material and preparation method thereof, lithium battery | |
| CN110165193A (en) | Hud typed high Ni-monocrystal nickel-cobalt lithium manganate cathode material of one kind and its preparation method and application | |
| CN104701530A (en) | Preparation method of in-situ doped and modified nickel cobalt manganese lithium oxide positive material | |
| CN103296249A (en) | Doped modified lithium nickel cobalt manganese material, preparation method thereof and lithium ion battery | |
| CN102280619A (en) | Preparation method of high-tap density spherical three-component anode material precursor | |
| CN109962233A (en) | A kind of class monocrystalline positive electrode of gradient type and preparation method thereof | |
| EP3611132A2 (en) | Method for preparing cathode active material | |
| KR20220061231A (en) | Lithium manganese rich material, its manufacturing method and application | |
| CN110165192A (en) | A kind of hud typed high voltage monocrystalline nickel-cobalt lithium manganate cathode material and its preparation method and application | |
| CN113871603B (en) | High-nickel ternary cathode material and preparation method thereof | |
| CN109888242A (en) | A kind of high-tap density cobalt nickel lithium manganate ternary material and preparation method thereof | |
| WO2024066445A1 (en) | Precursor for sodium-ion battery positive electrode material and preparation method therefor, sodium-ion battery positive electrode material, sodium-ion battery, and electrical device | |
| US11258063B2 (en) | Method for preparing positive electrode active material | |
| WO2023138220A1 (en) | Preparation method for positive electrode material precursor having large channel, and application thereof | |
| CN111933925A (en) | Grain boundary modified polycrystalline positive electrode material and preparation method thereof | |
| CN112062167A (en) | Micron-sized binary doped lithium-rich material and preparation method and application thereof | |
| CN114644363A (en) | High-nickel ternary precursor, positive electrode material and preparation method of precursor | |
| CN116053444A (en) | Doped layered anode material and application thereof in sodium ion battery | |
| CN108878807A (en) | High Ni-based quaternary positive electrode and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181123 |