CN106920934A - The preparation method of the codoping modified ternary precursor of cobalt magnesium and positive electrode based on high-nickel material - Google Patents
The preparation method of the codoping modified ternary precursor of cobalt magnesium and positive electrode based on high-nickel material Download PDFInfo
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- CN106920934A CN106920934A CN201710167988.4A CN201710167988A CN106920934A CN 106920934 A CN106920934 A CN 106920934A CN 201710167988 A CN201710167988 A CN 201710167988A CN 106920934 A CN106920934 A CN 106920934A
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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Abstract
The present invention relates to be based on the codoping modified ternary precursor of cobalt magnesium of high-nickel material and its preparation method of positive electrode, its chemical molecular formula is Li (NixCoyMgz)O2, wherein x+y+z=1, x >=0.85,0.14 >=y >=0.05,0.1 >=z >=0.01 belongs to lithium ion battery electrode material field.By in nickel cobalt magnesium mixed solution, ammoniacal liquor and NaOH mixed solution, sodium hydroxide solution cocurrent addition reactor, after coprecipitation reaction, precursor powder is obtained.And then obtain nickel cobalt magnesium tertiary cathode material.Wherein non-electroactive Mg2+, with " pillar stabilization ", Ni can be reduced with stable laminated structure2+With Li+Mixing, effectively improve the structural stability and chemical property of material.The present invention is simple to operate, can continuous batch production, product has the advantages that discharge capacity is big, good cycle, with economic worth and wide application prospect very high.
Description
Technical field
The present invention relates to technical field of lithium ion battery electrode, and in particular to a kind of cobalt magnesium based on high-nickel material is total to
The preparation method of doping vario-property ternary precursor and positive electrode
Background technology
Lithium ion battery as environmental protection of new generation, high-energy battery, with voltage it is high, capacity is big, memory-less effect and life-span
Long the advantages of, is widely used in the electronic products such as mobile phone, digital camera and notebook, it has also become battery industry development
One of emphasis.With the development of hybrid-electric car, pure electric vehicle and large-scale energy storage device, lithium ion battery of future generation is existed
Energy density, high rate performance and cycle life aspect propose requirement higher.In lithium ion battery, positive electrode is to determine
Determine the important component of battery fundamental characteristics.At present, the positive electrode of lithium ion battery mainly cobalt acid lithium (LiCoO2)、
LiMn2O4 (LiMn2O4), LiFePO4 (LiFePO4) and ternary material etc..The LiCoO of the ripe application of in the market2、LiMn2O4、
LiFePO4There is different aspect in material, it is impossible to while meeting above-mentioned requirements.
Tertiary cathode material includes using nickel cobalt manganese (Li (NixCoyMnz)O2, NCM) and nickel cobalt aluminium (Li (NixCoyAlz)O2,
NCA), with discharge capacity it is high, energy density is high, tap density is high and the relatively low advantage of cost and to receive people extensive
Concern.As CN105870409A Chinese patent literatures disclose a kind of preparation method of nickel-cobalt-manganternary ternary anode material, the party
Method is prepared with 1.0~3.0 micron order monocrystalline type positive electrodes and 18~22 microns by co-precipitation and nanospray experiment process
Li (the Ni of the secondary bulky grain of levelxCoyMnz)O2Material, has preferable chemical property for anode material for lithium-ion batteries.
CN106299347 Chinese patents disclose a kind of nickel cobalt aluminium ternary precursor and preparation method thereof and prepare positive electrode and
Be dissolved in the soluble-salt of Ni, Co in ammoniacal liquor by method, the method, and the ammonia for forming Ni, Co coordinates solion as complexing agent
Solution, adds complexing agent to form the cooperation solion of Al as silicon source solution in aluminum salt solution, can by coprecipitation process
Prepare the persursor material of the good sphericity of tri- kinds of element mixture homogeneities of Ni, Co and Al high, tap density and particle.Newest system
Meter, LiCoO2The market share has been decreased obviously, LiMn2O4And LiFePO4The market share expanded, and ternary material market
Share is but presented rapid increase trend, it was predicted that following 3 to 5 years, high-end ternary material electrokinetic cell will be presented that supply falls short of demand
Situation.But, it is poor still all to there is cyclical stability in NCM and NCA ternary materials, heat-resisting quantity difference and high rate performance is not good etc. asks
Topic, this is mainly due to Ni2+It is oxidized to Ni3+There is larger energy barrier, remaining Ni2+(0.069nm) is because of its ionic radius and Li+(0.076nm) it is close and enter Li layers.In charging process, the Ni in Li layers2+It is oxidized to the small Ni of ionic radius3+
(0.056nm) or Ni4+(0.048nm), causes layer structure to collapse, and in turn results in Li+It is difficult to increase of spreading and polarize.And
Under high voltage, take off lithium state NCM and NCA can and electrolyte there is side reaction, cause phase in version, make the layer structure of material gradually to
Spinel-like phase and NiO rock salt inversion of phases simultaneously discharge oxygen and substantial amounts of heat.Increase ternary material Ni contents or
Under hot environment above-mentioned side reaction can aggravate, penalty is aggravated.
At present in NCM and NCA ternary materials, Co/Mn and Co/Al doped chemicals all enter Ni layers, by stablizing nickel
The modes such as the bond strength between valence state and enhancing oxygen and metal ion, to improve structural stability, but still are difficult to avoid that because of Ni2+With Li+Mixing.Existing paper report：The Mg of non-electroactive2+, because of its ionic radius (0.072nm) and Li+It is similar to enter
Li, with " pillar " stabilization, the Mg in electrochemistry circulation2+Valence state remain constant, can be with stable laminated structure
Interlamellar spacing.But it is not related to Li (Ni at presentxCoyMgz)O2The patent literature of particularly nickelic (x >=85%) material, because
A kind of simple preparation technology for being adapted to mass produce of this exploitation, and prepare the nickelic Li (Ni of function admirablexCoyMgz)
O2Have great importance and application prospect.
The content of the invention
It is an object of the invention to provide a kind of nickel cobalt magnesium ternary precursor for preparing cobalt mg-doped and the preparation of positive electrode
Method, nickel cobalt magnesium ternary precursor and anode material spherical degree that the method is obtained are good, particle diameter distribution is narrower, three kinds of Elemental redistributions
Uniformly.
The present invention is adopted the following technical scheme that：
The codoping modified positive electrode of cobalt magnesium based on high-nickel material, its chemical molecular formula is Li (NixCoyMgz)O2, its
Middle x+y+z=1, x >=0.85,0.14 >=y >=0.05,0.1 >=z >=0.01.
A kind of preparation method of the codoping modified ternary precursor of cobalt magnesium based on high-nickel material, comprises the following steps：
1) preparing metal ion concentration is 0.5-6molL-1Nickel cobalt magnesium salt solution A, prepare ammoniacal liquor 0.5-7molL-1
With NaOH 0.5-10molL-1Mixed solution B, compound concentration is 1-6molL-1Single sodium hydroxide solution C.
2) to adding deionized water, mechanical agitation to use ammoniacal liquor 0.5-7molL in reactor-1With NaOH 0.5-
10mol·L-1Mixed solution B regulation pH, control system temperature is constant.
3) A, B, C are added in reactor simultaneously, with sodium hydroxide stabilized system pH.
4) reaction will be obtained after terminating precipitation filtering, washing, 4-12h is dried in 70 DEG C of -200 DEG C of vacuum drying chambers,
Obtain presoma NixCoyMgz(OH)2。
The codoping modified ternary precursor of the described cobalt magnesium based on high-nickel material prepares nickel cobalt magnesium tertiary cathode material
Method, by nickel cobalt magnesium presoma NixCoyMgz(OH)2It is well mixed with lithium salts, is calcined in tube furnace, calcination procedure is first to exist
300-600 DEG C of calcining 2-10h of low temperature, then 6-20h is calcined at 600-900 DEG C, calcination atmosphere is air or oxygen, material nature
Room temperature is cooled to, the product grinding sieving that will be obtained obtains the nickelic nickel tertiary cathode material of cobalt magnesium codope.
The preparation method of the described codoping modified ternary precursor of cobalt magnesium based on high-nickel material, step 1) in nickel salt,
The mol ratio of cobalt salt and magnesium salts is (0.85-0.94)：(0.05-0.14)：(0.01-0.1).
The preparation method of the described codoping modified ternary precursor of cobalt magnesium based on high-nickel material, step 2) in stirring
Speed is 400-850rpmmin-1, system temperature control is at 30-70 DEG C.
The preparation method of the described codoping modified ternary precursor of cobalt magnesium based on high-nickel material, is controlled using peristaltic pump
Sodium hydroxide solution enters flow quantity so that the pH of system is fixed on 9-12.
The preparation method of the described codoping modified ternary precursor of cobalt magnesium based on high-nickel material, step 1) used by metal
Salt is one or more in sulfate, nitrate, chlorate.
The method of described preparation nickel cobalt magnesium tertiary cathode material, the heating rate in roasting process is 1-15 DEG C of min-1。
The method of described preparation nickel cobalt magnesium tertiary cathode material, lithium salts used is lithium nitrate, lithium carbonate, lithium hydroxide
One or more, elemental lithium compares Li with nickel, cobalt, the amount of the material of magnesium elements in presoma:(Ni+Co+Mg) it is 0.95-1.
Beneficial effects of the present invention：
(1) the nickel cobalt magnesium ternary material tap density for preparing is high, and particle good sphericity, particle diameter distribution is narrower.
(2) the preparation method technique is relatively simple, and each parameter is specific adjustable controllable in production, and energy consumption is relatively low, is especially suitable for
In a large amount of, the continuous prodution of industry.
(3) doping of appropriate divalent metal magnesium ion, can preferably reduce Li+With Ni2+Mixing, maintain discharge and recharge
During stability so that the characteristic of high-nickel material high power capacity is maintained, by the method prepare tertiary cathode material,
Can be widely applied to high specific energy secondary cell field.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the nickel cobalt magnesium presoma of the gained of the embodiment of the present invention 2.
Fig. 2 is the scanning electron microscope (SEM) photograph of the nickel cobalt magnesium tertiary cathode material of the gained of the embodiment of the present invention 2, as seen from the figure by roasting
After burning, product still maintains the spherical morphology of presoma.
Fig. 3 is the X-ray diffractogram of the nickel cobalt magnesium presoma of the gained of the embodiment of the present invention 2, finds each diffraction maximum in figure
Standard PDF cards with nickel hydroxide are consistent.
Fig. 4 is the X-ray diffractogram of the nickel cobalt magnesium tertiary cathode material of the gained of the embodiment of the present invention 2, each in discovery figure
Diffraction maximum is consistent with the standard PDF cards of lithium nickelate.
Fig. 5 is that CR2032 buttons electricity is assembled into as positive pole using the nickel cobalt magnesium ternary material of the gained of the embodiment of the present invention 2
Chi Hou, the first circle charging and discharging curve under 0.1C multiplying powers that test is obtained.
Fig. 6 is that CR2032 buttons electricity is assembled into as positive pole using the nickel cobalt magnesium ternary material of the gained of the embodiment of the present invention 2
Chi Hou, the cycle performance under 1C multiplying powers that test is obtained.
Fig. 7 is the preparation flow figure of nickel cobalt magnesium tertiary cathode material of the present invention.
Specific embodiment
Further the present invention will be explained by specific example below, example below is only said as one kind
It is bright, and the limitation to scope in one's power of the invention is understood not to, distribute bright protection domain and be also not necessarily limited to following implementation
Example.
Embodiment 1
Step (1)：Configuration transition metal ion solution, its concentration is 0.5molL-1, wherein nickel cobalt magnesium salts be nickel sulfate,
The mixture of cobaltous sulfate, magnesium sulfate, nickel ion, cobalt ions, the mol ratio of magnesium ion are 0.89:0.05:0.06.It is separately dense with ammoniacal liquor
It is 2molL to spend-1, naoh concentration be 2molL-1Mixed solution and naoh concentration be 1molL-1Solution.
Three of the above solution is placed on agitator and is sufficiently stirred, solute is fully dissolved.
Step (2)：To 300ml deionized waters are added in the reactor of sealing, the mixing speed for setting agitating paddle is
650rpm·min-1, by system temperature control at 40 DEG C, appropriate concentrated ammonia liquor initial adjustment pH is instilled, then adjusted with sodium hydroxide solution
PH to 10.5.After after stable system, transition metal ion solution, ammoniacal liquor and sodium hydroxide solution are pumped into simultaneously using peristaltic pump
Reactor, period, by adjusting the feed speed of sodium hydroxide solution, makes pH stabilizations 10.5.
Step (3)：After charging is finished, it is aged 1 hour, partial reaction liquid, suction filtration, drying is taken out from reflection kettle.
Step (4)：Abundant dry nickel cobalt magnesium presoma 0.3g is taken, is fully mixed with lithium carbonate using agate mortar
Close, wherein Li:(Ni+Co+Mg) oxygen atmosphere=1.07, is passed through in tube furnace, with 3 DEG C of min-1Programming rate rise to
550 DEG C of insulation 5h, are warming up to 700 DEG C with same heating rate again afterwards, after insulation 16h, are naturally cooling to room temperature, are calcined
To product by grinding, sieving obtain nickel cobalt magnesium tertiary cathode material.
Embodiment 2
Step (1)：Configuration transition metal ion solution, its concentration is 3molL-1, wherein nickel cobalt magnesium salts is nickel chloride, chlorine
Change cobalt, the mixture of magnesium chloride, nickel ion, cobalt ions, the mol ratio of magnesium ion are 0.9:0.05:0.05.Separately match somebody with somebody ammonia concn
It is 0.5molL-1, naoh concentration be 0.5molL-1Mixed solution and naoh concentration be 4molL-1It is molten
Liquid.Three of the above solution is placed on agitator and is sufficiently stirred, solute is fully dissolved.
Step (2)：To 300ml deionized waters are added in the reactor of sealing, the mixing speed for setting agitating paddle is
800rpm·min-1, by system temperature control at 50 DEG C, appropriate concentrated ammonia liquor initial adjustment pH is instilled, then adjusted with sodium hydroxide solution
PH to 10.8.After after stable system, transition metal ion solution, ammoniacal liquor and sodium hydroxide solution are pumped into simultaneously using peristaltic pump
Reactor, period, by adjusting the feed speed of sodium hydroxide solution, makes pH stabilizations 10.8.
Step (3)：After charging is finished, it is aged 1 hour, partial reaction liquid, suction filtration, drying is taken out from reflection kettle.
Step (4)：Abundant dry nickel cobalt magnesium presoma 0.5g is taken, is fully mixed with lithium carbonate using agate mortar
Close, wherein Li:(Ni+Co+Mg) oxygen atmosphere=1.02, is passed through in tube furnace, with 5 DEG C of min-1Programming rate rise to
550 DEG C of insulation 5h, are warming up to 700 DEG C with same heating rate again afterwards, after insulation 12h, are naturally cooling to room temperature, are calcined
To product by grinding, sieving obtain nickel cobalt magnesium tertiary cathode material.
Embodiment 3
Step (1)：Configuration transition metal ion solution, its concentration is 1molL-1, wherein nickel cobalt magnesium salts is nickel sulfate, sulphur
The mixture of sour cobalt, magnesium sulfate, nickel ion, cobalt ions, the mol ratio of magnesium ion are 0.85:0.1:0.05.Separately match somebody with somebody ammonia concn
It is 3molL-1, naoh concentration be 3molL-1Mixed solution and naoh concentration be 2molL-1Solution.Will
Three of the above solution is placed on agitator and is sufficiently stirred, and solute is fully dissolved.
Step (2)：To 300ml deionized waters are added in the reactor of sealing, the mixing speed for setting agitating paddle is
750rpm·min-1, by system temperature control at 50 DEG C, appropriate concentrated ammonia liquor initial adjustment pH is instilled, then adjusted with sodium hydroxide solution
PH to 10.6.After after stable system, transition metal ion solution, ammoniacal liquor and sodium hydroxide solution are pumped into simultaneously using peristaltic pump
Reactor, period, by adjusting the feed speed of sodium hydroxide solution, makes pH stabilizations 10.6.
Step (3)：After charging is finished, it is aged 1 hour, partial reaction liquid, suction filtration, drying is taken out from reflection kettle.
Step (4)：Abundant dry nickel cobalt magnesium presoma 0.4g is taken, is fully mixed with lithium carbonate using agate mortar
Close, wherein Li:(Ni+Co+Mg) oxygen atmosphere=1.05, is passed through in tube furnace, with 4 DEG C of min-1Programming rate rise to
450 DEG C of insulation 6h, are warming up to 650 DEG C with same heating rate again afterwards, after insulation 18h, are naturally cooling to room temperature, are calcined
To product by grinding, sieving obtain nickel cobalt magnesium tertiary cathode material.
Embodiment 4
Step (1)：Configuration transition metal ion solution, its concentration is 2molL-1, wherein nickel cobalt magnesium salts is nickel sulfate, sulphur
The mixture of sour cobalt, magnesium sulfate, nickel ion, cobalt ions, the mol ratio of magnesium ion are 0.9:0.05:0.05.Separately match somebody with somebody ammonia concn
It is 1molL-1, naoh concentration be 1molL-1Mixed solution and naoh concentration be 3molL-1Solution.Will
Three of the above solution is placed on agitator and is sufficiently stirred, and solute is fully dissolved.
Step (2)：To 300ml deionized waters are added in the reactor of sealing, the mixing speed for setting agitating paddle is
850rpm·min-1, by system temperature control at 55 DEG C, appropriate concentrated ammonia liquor initial adjustment pH is instilled, then adjusted with sodium hydroxide solution
PH to 10.9.After after stable system, transition metal ion solution, ammoniacal liquor and sodium hydroxide solution are pumped into simultaneously using peristaltic pump
Reactor, period, by adjusting the feed speed of sodium hydroxide solution, makes pH stabilizations 10.9.
Step (3)：After charging is finished, it is aged 1 hour, partial reaction liquid, suction filtration, drying is taken out from reflection kettle.
Step (4)：Abundant dry nickel cobalt magnesium presoma 0.6g is taken, is fully mixed with lithium carbonate using agate mortar
Close, wherein Li:(Ni+Co+Mg) oxygen atmosphere=1.1, is passed through in tube furnace, with 2 DEG C of min-1Programming rate rise to 350
DEG C insulation 4h, is warming up to 750 DEG C with same heating rate again afterwards, after insulation 12h, is naturally cooling to room temperature, and roasting is obtained
Product by grinding, sieving obtain nickel cobalt magnesium tertiary cathode material.
Embodiment 5
Step (1)：Configuration transition metal ion solution, its concentration is 0.5molL-1, wherein nickel cobalt magnesium salts be nickel nitrate,
The mixture of cobalt nitrate, magnesium nitrate, nickel ion, cobalt ions, the mol ratio of magnesium ion are 0.9:0.07:0.03.It is separately dense with ammoniacal liquor
It is 2molL to spend-1, naoh concentration be 2molL-1Mixed solution and naoh concentration be 4molL-1Solution.
Three of the above solution is placed on agitator and is sufficiently stirred, solute is fully dissolved.
Step (2)：To 300ml deionized waters are added in the reactor of sealing, the mixing speed for setting agitating paddle is
700rpm·min-1, by system temperature control at 60 DEG C, appropriate concentrated ammonia liquor initial adjustment pH is instilled, then adjusted with sodium hydroxide solution
PH to 10.7.After after stable system, transition metal ion solution, ammoniacal liquor and sodium hydroxide solution are pumped into simultaneously using peristaltic pump
Reactor, period, by adjusting the feed speed of sodium hydroxide solution, makes pH stabilizations 10.7.
Step (3)：After charging is finished, it is aged 1 hour, partial reaction liquid, suction filtration, drying is taken out from reflection kettle.
Step (4)：Abundant dry nickel cobalt magnesium presoma 0.4g is taken, is fully mixed with lithium carbonate using agate mortar
Close, wherein Li:(Ni+Co+Mg) oxygen atmosphere=1.09, is passed through in tube furnace, with 4 DEG C of min-1Programming rate rise to
400 DEG C of insulation 5h, are warming up to 600 DEG C with same heating rate again afterwards, after insulation 1h, are naturally cooling to room temperature, are calcined
To product by grinding, sieving obtain nickel cobalt magnesium tertiary cathode material.
In sum, above example is only that principle of the invention and implementation method are illustrated, and is not intended to limit this
The protection domain of invention.It should be pointed out that it will be apparent to one skilled in the art that, do not departing from the premise of the principle of the invention
Under, any modification, equivalent substitution and improvements made for the present invention etc. should be included within the scope of the present invention.
Claims (9)
1. the codoping modified positive electrode of cobalt magnesium of high-nickel material is based on, and its chemical molecular formula is Li (NixCoyMgz)O2, wherein x+
Y+z=1, x >=0.85,0.14 >=y >=0.05,0.1 >=z >=0.01.
2. a kind of preparation method of the codoping modified ternary precursor of cobalt magnesium based on high-nickel material, it is characterised in that including with
Lower step：
1) preparing metal ion concentration is 0.5-6molL-1Nickel cobalt magnesium salt solution A, prepare ammoniacal liquor 0.5-7molL-1And hydrogen
Sodium oxide molybdena 0.5-10molL-1Mixed solution B, compound concentration is 1-6molL-1Single sodium hydroxide solution C；
2) to adding deionized water, mechanical agitation to use ammoniacal liquor 0.5-7molL in reactor-1With NaOH 0.5-10mol
L-1Mixed solution B regulation pH, control system temperature is constant；
3) A, B, C are added in reactor simultaneously, with sodium hydroxide stabilized system pH；
4) reaction will be obtained after terminating precipitation filtering, washing, 4-12h is dried in 70 DEG C of -200 DEG C of vacuum drying chambers, is obtained
Presoma NixCoyMgz(OH)2。
3. nickel cobalt magnesium three is prepared using the codoping modified ternary precursor of the cobalt magnesium based on high-nickel material described in claims 2
The method of first positive electrode, it is characterised in that by nickel cobalt magnesium presoma NixCoyMgz(OH)2It is well mixed with lithium salts, in tubular type
Calcined in stove, calcination procedure is first in 300-600 DEG C of calcining 2-10h of low temperature, then calcines 6-20h, calcination atmosphere at 600-900 DEG C
It is air or oxygen, material is naturally cooling to room temperature, the product grinding sieving that will be obtained obtains the nickelic nickel of cobalt magnesium codope
Tertiary cathode material.
4. the preparation method of the codoping modified ternary precursor of cobalt magnesium based on high-nickel material according to claim 2, its
Be characterised by step 1) in nickel salt, cobalt salt and magnesium salts mol ratio be (0.85-0.94)：(0.05-0.14)：(0.01-0.1).
5. the preparation method of the codoping modified ternary precursor of cobalt magnesium based on high-nickel material according to claim 2, its
Be characterised by step 2) in mixing speed be 400-850rpmmin-1, system temperature control is at 30-70 DEG C.
6. the preparation method of the codoping modified ternary precursor of cobalt magnesium based on high-nickel material according to claim 2, its
It is characterised by entering flow quantity using peristaltic pump control sodium hydroxide solution so that the pH of system is fixed on 9-12.
7. the preparation method of the codoping modified ternary precursor of cobalt magnesium based on high-nickel material according to claim 2, its
Be characterised by step 1) used by slaine be sulfate, nitrate, chlorate in one or more.
8. it is according to claim 3 prepare nickel cobalt magnesium tertiary cathode material method, it is characterised in that in roasting process
Heating rate is 1-15 DEG C of min-1。
9. it is according to claim 3 prepare nickel cobalt magnesium tertiary cathode material method, it is characterised in that lithium salts used be nitre
Sour lithium, lithium carbonate, one or more of lithium hydroxide, nickel, cobalt, the amount of the material of magnesium elements compare Li in elemental lithium and presoma:
(Ni+Co+Mg) it is 0.95-1.5.
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| CN109626447A (en) * | 2018-12-13 | 2019-04-16 | 南开大学 | Nickelic anode material for lithium-ion batteries of a kind of concentration gradient magnesium doping and preparation method thereof |
| CN110867574A (en) * | 2019-11-07 | 2020-03-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of high-nickel ternary material (NCW), product and application thereof |
| CN111924899A (en) * | 2020-08-11 | 2020-11-13 | 中钢集团南京新材料研究院有限公司 | Method for preparing nickel-cobalt-iron-aluminum-magnesium five-element high-entropy material, product and application |
| CN112366309A (en) * | 2020-11-23 | 2021-02-12 | 中伟新材料股份有限公司 | Magnesium-doped nickel-cobalt binary precursor and preparation method thereof, lithium ion battery positive electrode material and lithium ion battery |
| CN114655998A (en) * | 2022-03-01 | 2022-06-24 | 西安理工大学 | Preparation method of high-nickel ternary positive electrode precursor |
| US11923542B2 (en) | 2017-12-21 | 2024-03-05 | Research Institute Of Industrial Science & Technology | Positive active material for lithium rechargeable battery, manufacturing method thereof, and lithium rechargeable battery including same positive active material |
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| CN107293695A (en) * | 2017-07-28 | 2017-10-24 | 荆门市格林美新材料有限公司 | A kind of method of pair of kettle Fast back-projection algorithm ternary anode material of lithium battery presoma |
| CN107293695B (en) * | 2017-07-28 | 2019-12-10 | 荆门市格林美新材料有限公司 | method for rapidly synthesizing ternary lithium battery positive electrode material precursor by double kettles |
| US11923542B2 (en) | 2017-12-21 | 2024-03-05 | Research Institute Of Industrial Science & Technology | Positive active material for lithium rechargeable battery, manufacturing method thereof, and lithium rechargeable battery including same positive active material |
| CN107983288A (en) * | 2018-01-03 | 2018-05-04 | 常州九朝新能源科技有限公司 | On-line monitoring intelligent linkage reaction kettle |
| CN109626447A (en) * | 2018-12-13 | 2019-04-16 | 南开大学 | Nickelic anode material for lithium-ion batteries of a kind of concentration gradient magnesium doping and preparation method thereof |
| CN110867574A (en) * | 2019-11-07 | 2020-03-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of high-nickel ternary material (NCW), product and application thereof |
| CN111924899A (en) * | 2020-08-11 | 2020-11-13 | 中钢集团南京新材料研究院有限公司 | Method for preparing nickel-cobalt-iron-aluminum-magnesium five-element high-entropy material, product and application |
| CN112366309A (en) * | 2020-11-23 | 2021-02-12 | 中伟新材料股份有限公司 | Magnesium-doped nickel-cobalt binary precursor and preparation method thereof, lithium ion battery positive electrode material and lithium ion battery |
| CN114655998A (en) * | 2022-03-01 | 2022-06-24 | 西安理工大学 | Preparation method of high-nickel ternary positive electrode precursor |
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