CN108899531A - A kind of preparation method of Phosphate coating nickel cobalt aluminium tertiary cathode material - Google Patents
A kind of preparation method of Phosphate coating nickel cobalt aluminium tertiary cathode material Download PDFInfo
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- 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 invention discloses a kind of preparation methods of Phosphate coating nickel cobalt aluminium tertiary cathode material, it is using nickel cobalt aluminium tertiary cathode material as kernel, phosphate is coated on the surface of the kernel, and chelating agent is added during cladding, to promote Phosphate coating on nickel cobalt aluminium tertiary cathode material surface.Positive electrode of the present invention after Phosphate coating possesses higher Ion transfer ability and electron transmission ability, and the material after cladding inhibits the side reaction between positive electrode and electrolyte, and cycle performance and capacity retention ratio are significantly improved.
Description
Technical field
The invention belongs to lithium ion battery technology and electrochemical fields, and in particular to a kind of Phosphate coating nickel cobalt aluminium ternary
The preparation method of positive electrode.
Background technique
As energy problem becomes increasingly conspicuous, the substance for finding the alternative ore energy is become as the eager concern of people.
Battery becomes the research emphasis that people develop and utilize the energy as important energy storage device.Wherein lithium ion battery is last century
The sustainable use battery to grow up the nineties, because its energy density height, memory-less effect, high output voltage and self discharge compared with
It is small so being most widely used in the electrical equipments such as laptop, mobile phone.Lithium ion battery is to various electronic at present
The development of the automotive fields such as vehicle and hybrid electric vehicle will become the core of power battery on new-energy automobile.Wherein ternary is being just
Pole material has at low cost, the advantages that discharge capacity is big, stable structure, it has also become novel lithium most promising at present from
One of sub- cell positive material.
The method of synthesis NCA mainly includes high temperature solid-state method, coprecipitation, sol-gal process, spray drying process etc. at present.
High temperature solid-state method preparation process is simple, at low cost, but reaction raw materials mixing uniformity is poor, and granule-morphology and the regularity of distribution are poor
Cause chemical property poor；Coprecipitation process is relatively easy, resulting materials element, even particle size distribution, and capacity is high, circulation
Performance is good.But the influence factor that synthesis process needs to control is more, and operating procedure is complicated；Sol-gal process can be in a short time
Realize the Elemental redistribution of molecular level, reaction is easier to carry out, and temperature is lower.But the cost of raw material is higher, and gel contains largely
Gas escapes and generates contraction micropore in the drying process；The stoichiometric ratio of the easily controllable product of spray drying process, it is obtained
Product is purer, but cost of equipment is higher, and the thermal efficiency is lower.
The most popular method for synthesizing NCA at this stage is using coprecipitation, generally first by nickel salt, cobalt salt and aluminium salt and complexing
Agent ammonium hydroxide, lye NaOH cocurrent are added to reaction kettle and are prepared into divalent co-precipitation presoma, be then sintered with lithium.But it prepares
The disadvantages of that there is reversible capacities is low for material, and high rate performance is poor.
Summary of the invention
The present invention is intended to provide a kind of preparation method of Phosphate coating nickel cobalt aluminium tertiary cathode material, is chelated by addition
Agent promotes Phosphate coating positive electrode.Positive electrode of the present invention after Phosphate coating possesses higher Ion transfer energy
Power and electron transmission ability, the material after cladding inhibit the side reaction between positive electrode and electrolyte, cycle performance and appearance
Amount conservation rate is significantly improved.
Phosphate coating nickel cobalt aluminium tertiary cathode material of the present invention, be using nickel cobalt aluminium tertiary cathode material as kernel,
The surface of the kernel is coated with phosphate, and adds chelating agent during cladding, to promote Phosphate coating in nickel cobalt
Aluminium tertiary cathode material surface.
The general formula of the nickel cobalt aluminium tertiary cathode material is LiNi1-x-yCoxAlyO2, wherein 0 x≤0.2 <, 0 < y≤
0.05。
The phosphate is Ma(PO4)b, at least one of M Fe, Ni, Al, Mg, Zn, Co.
The preparation method of Phosphate coating nickel cobalt aluminium tertiary cathode material of the present invention, includes the following steps：
Step 1：Using coprecipitation, nickel cobalt aluminium presoma is prepared under an inert atmosphere；
Step 2：Nickel cobalt aluminium presoma and lithium source made from step 1 are mixed and ground, the first mixture is obtained；
Step 3：The first mixture of gained is warming up to 450 in oxygen-supplying tube formula furnace with the heating rate of 2~5 DEG C/min~
It 500 DEG C, keeps the temperature 6h, then be warming up to 750~850 DEG C with the heating rate of 2~5 DEG C/min, is ground up, sieved after furnace cooling to obtain the final product
Ternary cathode material of lithium ion battery LiNi1-x-yCoxAlyO2(i.e. NCA material)；
Step 4：The source M, phosphorus source and chelating agent are weighed, LiNi is added after the source M and chelating agent are dissolved with aqueous solvent1-x- yCoxAlyO2, phosphorus source and magnetic agitation 1-5h is then added dropwise, centrifuge separation is subsequently placed in Muffle furnace and keeps the temperature in 400~500 DEG C
5~8h is to get Phosphate coating tertiary cathode material.
In step 1, the nickel cobalt aluminium presoma is at least one of nickel cobalt aluminium hydroxide, nickel cobalt aluminium carbonate.
In step 1, the inert atmosphere is at least one of nitrogen, argon gas.
In step 2, the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium acetate.
In step 4, the source M is at least one of sulfate, nitrate；Phosphorus source is ammonium dihydrogen phosphate, phosphoric acid
At least one of hydrogen diammonium, ammonium phosphate；The chelating agent is at least one of EDETATE SODIUM, PVP.
In step 4, the quality of phosphorus source is the 1~5% of tertiary cathode material quality；Metal ion in chelating agent and the source M
Molar ratio is 1:1.
To reduce influence of the aqueous solvent to NCA material, in terms of 1g NCA mass, the overall control of aqueous solvent in step 4≤
10g。
The present invention promotes cladding, reversible capacity of the made positive electrode between 2.8-4.3V by adding appropriate chelating agent
It is modified that there is good cyclical stability and high rate performance up to 152.87mAh/g.
The present invention promotes metal ion more evenly closely to combine on the surface of the material by the coordination ability of chelating agent, then
Uniform Phosphate coating layer is generated after phosphorus source is added, to inhibit the side reaction between positive electrode and electrolyte, is promoted
Chemical property.
Detailed description of the invention
Fig. 1 is the TEM figure of NCA positive electrode prepared by the embodiment of the present invention 7；As can be seen from Figure 1 phosphate success
It is coated on ternary material surface, thickness about 5-8nm.
Fig. 2 is the embodiment of the present invention 1, embodiment 2, the XRD diagram of NCA positive electrode prepared by embodiment 3；It can from Fig. 2
To find out still there is typical α-NaFeO under condition of different pH2Structure.
Fig. 3 is the embodiment of the present invention 1, embodiment 2, the cycle performance figure of NCA positive electrode prepared by embodiment 3；From Fig. 3
In it can be seen that pH be 11.5 when best performance, material first discharge specific capacity be 131.04mAh/g, 50 circle circulation after discharge hold
Amount is 116.78mAh/g, capacity retention ratio 89.12%.
Fig. 4 is the embodiment of the present invention 3, embodiment 4, the cycle performance figure of NCA positive electrode prepared by embodiment 5；From Fig. 4
In it can be seen that 850 DEG C of best performances, capacity retention ratio is 77.79% after 100 circle circulations.
Fig. 5 be the embodiment of the present invention 6, embodiment 7, difference magnesium phosphate covering amount prepared by embodiment 8 NCA positive electrode
XRD diagram；As can be seen from Figure 5 coating does not cause material crystal structure to change.
Fig. 6 be the embodiment of the present invention 6, embodiment 7, difference magnesium phosphate covering amount prepared by embodiment 8 NCA positive electrode
Cycle performance figure；As can be seen from Figure 6 2%Mg3(PO4)2@NCA best performance, capacity retention ratio is after 100 circles recycle
88.77%.
Fig. 7 be the embodiment of the present invention 6, embodiment 7, difference magnesium phosphate covering amount prepared by embodiment 8 NCA positive electrode
High rate performance figure.As can be seen from Figure 7 2%Mg3(PO4)2@NCA high rate performance is substantially better than other covering amount materials.
Specific embodiment
To make technical solution of the present invention, more clearly in conjunction with attached drawing, the invention will be further described.
Embodiment 1：
1, using nickel nitrate, cobalt nitrate, aluminum nitrate as raw material, by Ni：Co：Al=80：15：5 molar ratio
The mixed metal solution of 100mL0.5mol/L, while preparing the ammonia spirit of 200mL 1mol/L, the NaOH of 100mL 3mol/L
Solution.Using four-hole boiling flask as reaction kettle, the ammonia spirit of 100mL1mol/L is placed in flask as bottom liquid, with thunder magnetic PHS-
3E pH electrode carries out pH real-time monitoring, with nitrogen as protection gas.Sample introduction speed is controlled by peristaltic pump to react in reaction kettle
It is aged 20h, whole-process control pH=10.5, filtration washing, which is dried, is made nickel cobalt aluminium hydroxide precursor；
2, according to molar ratio Li：M (metal cation, i.e. Ni, Co and Al)=1.05：1 weighs LiOHH2O, grinding are mixed
It contains corundum boat after closing uniformly to be placed in tube furnace, logical oxygen is warming up to 500 DEG C of heat preservation 6h with 2 DEG C/min heating rate, so
It grinds after being warming up to 750 DEG C of heat preservation 12h coolings afterwards with 2 DEG C/min heating rate up to NCA material；
3, by NCA material, conductive agent acetylene black, binder PVDF in mass ratio 8：1：1 ratio mixed grinding half an hour,
Dropwise addition NMP (N-methyl pyrrolidones) is adjusted to paste and is coated uniformly on aluminium foil, roll-in punching after drying, and positive plate is made；With
Metal lithium sheet is cathode, using microporous polypropylene membrane as diaphragm, with the LiPF of 1mol/L6For electrolyte, it is assembled into glove box
CR2032 type battery.
Assembled battery is subjected to 0.1C constant current charge-discharge test at room temperature, voltage range is 2.8~4.3V, the material
Material first discharge specific capacity is 126.75mAh/g, and discharge capacity is 95.89mAh/g after 50 circle circulations, and capacity retention ratio is
75.65%
Embodiment 2：
1, using nickel nitrate, cobalt nitrate, aluminum nitrate as raw material, by Ni：Co：Al=80：15：5 molar ratio
The mixed metal solution of 100mL0.5mol/L, while preparing the ammonia spirit of 200mL 1mol/L, the NaOH of 100mL 3mol/L
Solution.Using four-hole boiling flask as reaction kettle, the ammonia spirit of 100mL1mol/L is placed in flask as bottom liquid, with thunder magnetic PHS-
3E pH electrode carries out pH real-time monitoring, with nitrogen as protection gas, controls sample introduction speed by peristaltic pump and reacts in reaction kettle
It is aged 20h, whole-process control pH=11, filtration washing, which is dried, is made nickel cobalt aluminium hydroxide precursor；
2, according to molar ratio Li：M (metal cation, i.e. Ni, Co and Al)=1.05：1 weighs LiOHH2O, grinding are mixed
It contains corundum boat after closing uniformly to be placed in tube furnace, logical oxygen is warming up to 500 DEG C of heat preservation 6h with 2 DEG C/min heating rate, so
It grinds after being warming up to 750 DEG C of heat preservation 12h coolings afterwards with 2 DEG C/min heating rate up to NCA material；
3, by NCA material, conductive agent acetylene black, binder PVDF in mass ratio 8：1：1 mixed grinding half an hour was added dropwise
NMP (N-methyl pyrrolidones) is adjusted to paste and is coated uniformly on aluminium foil, roll-in punching after drying, and positive plate is made；With metal
Lithium piece is cathode, using microporous polypropylene membrane as diaphragm, with the LiPF of 1mol/L6For electrolyte, it is assembled into glove box
CR2032 type battery.
Assembled battery is subjected to 0.1C constant current charge-discharge test at room temperature, voltage range is 2.8~4.3V, the material
Material first discharge specific capacity is 117.02mAh/g, and discharge capacity is 69.41mAh/g after 50 circle circulations, and capacity retention ratio is
59.31%.
Embodiment 3：
1, using nickel nitrate, cobalt nitrate, aluminum nitrate as raw material, by Ni：Co：Al=80：15：5 molar ratio
The mixed metal solution of 100mL0.5mol/L, while preparing the ammonia spirit of 200mL 1mol/L, the NaOH of 100mL 3mol/L
Solution.Using four-hole boiling flask as reaction kettle, the ammonia spirit of 100mL1mol/L is placed in flask as bottom liquid, with thunder magnetic PHS-
3E pH electrode carries out pH real-time monitoring, with nitrogen as protection gas.Sample introduction speed is controlled by peristaltic pump to react in reaction kettle
It is aged 20h, whole-process control pH=11.5, filtration washing, which is dried, is made nickel cobalt aluminium hydroxide precursor；
2, according to molar ratio Li：M (metal cation, i.e. Ni, Co and Al)=1.05：1 weighs LiOHH2O, grinding are mixed
It contains corundum boat after closing uniformly to be placed in tube furnace, logical oxygen is warming up to 500 DEG C of heat preservation 6h with 2 DEG C/min heating rate, so
It grinds after being warming up to 750 DEG C of heat preservation 12h coolings afterwards with 2 DEG C/min heating rate up to NCA material；
3, by NCA material, conductive agent acetylene black, binder PVDF in mass ratio 8：1：1 mixed grinding half an hour was added dropwise
NMP (N-methyl pyrrolidones) is adjusted to paste and is coated uniformly on aluminium foil, roll-in punching after drying, and positive plate is made；With metal
Lithium piece is cathode, using microporous polypropylene membrane as diaphragm, with the LiPF of 1mol/L6For electrolyte, it is assembled into glove box
CR2032 type battery.
Assembled battery is subjected to 0.1C constant current charge-discharge test at room temperature, voltage range is 2.8~4.3V, the material
Material first discharge specific capacity is 131.04mAh/g, and discharge capacity is 116.78mAh/g after 50 circle circulations, and capacity retention ratio is
89.12%.
Embodiment 4：
1, using nickel nitrate, cobalt nitrate, aluminum nitrate as raw material, by Ni：Co：Al=80：15：5 molar ratio
The mixed metal solution of 100mL0.5mol/L, while preparing the ammonia spirit of 200mL 1mol/L, the NaOH of 100mL 3mol/L
Solution.Using four-hole boiling flask as reaction kettle, the ammonia spirit of 100mL1mol/L is placed in flask as bottom liquid, with thunder magnetic PHS-
3E pH electrode carries out pH real-time monitoring, with nitrogen as protection gas, controls sample introduction speed by peristaltic pump and reacts in reaction kettle
It is aged 20h, whole-process control pH=11.5, filtration washing, which is dried, is made nickel cobalt aluminium hydroxide precursor；
2, according to molar ratio Li：M (metal cation, i.e. Ni, Co and Al)=1.05：1 weighs LiOHH2O, grinding are mixed
It contains corundum boat after closing uniformly to be placed in tube furnace, logical oxygen is warming up to 500 DEG C of heat preservation 6h with 2 DEG C/min heating rate, so
It grinds after being warming up to 800 DEG C of heat preservation 12h coolings afterwards with 2 DEG C/min heating rate up to NCA material；
3, by NCA material, conductive agent acetylene black, binder PVDF in mass ratio 8：1：1 grinding half an hour, NMP (nitrogen is added dropwise
Methyl pyrrolidone) it is adjusted to paste and is coated uniformly on aluminium foil, positive plate is made in roll-in punching after drying；It is with metal lithium sheet
Cathode, using microporous polypropylene membrane as diaphragm, with the LiPF of 1mol/L6For electrolyte, CR2032 type electricity is assembled into glove box
Pond.
Assembled battery is subjected to 0.1C constant current charge-discharge test at room temperature, voltage range is 2.8~4.3V, the material
Material first discharge specific capacity is 141.28mAh/g, and discharge capacity is 100.83mAh/g after 100 circle circulations, and capacity retention ratio is
71.37%.
Embodiment 5：
1, using nickel nitrate, cobalt nitrate, aluminum nitrate as raw material, by Ni：Co：Al=80：15：5 molar ratio
The mixed metal solution of 100mL0.5mol/L, while preparing the ammonia spirit of 200mL 1mol/L, the NaOH of 100mL 3mol/L
Solution.Using four-hole boiling flask as reaction kettle, the ammonia spirit of 100mL1mol/L is placed in flask as bottom liquid, with thunder magnetic PHS-
3E pH electrode carries out pH real-time monitoring, with nitrogen as protection gas.Sample introduction speed is controlled by peristaltic pump to react in reaction kettle
It is aged 20h, whole-process control pH=11.5, filtration washing, which is dried, is made nickel cobalt aluminium hydroxide precursor；
2, according to molar ratio Li：M (metal cation, i.e. Ni, Co and Al)=1.05：1 weighs LiOHH2O, grinding are mixed
Contain corundum boat after closing uniformly and be placed in tube furnace and lead to oxygen 500 DEG C of heat preservation 6h are warming up to 2 DEG C/min heating rate, then with
2 DEG C/min heating rate is ground after being warming up to 850 DEG C of heat preservation 12h coolings up to NCA material.
3, by NCA material, conductive agent acetylene black, binder PVDF in mass ratio 8：1：1 grinding half an hour, NMP (nitrogen is added dropwise
Methyl pyrrolidone) it is adjusted to paste and is coated uniformly on aluminium foil, positive plate is made in roll-in punching after drying；It is with metal lithium sheet
Cathode, using microporous polypropylene membrane as diaphragm, with the LiPF of 1mol/L6For electrolyte, CR2032 type electricity is assembled into glove box
Pond.
Assembled battery is subjected to 0.1C constant current charge-discharge test at room temperature, voltage range is 2.8~4.3V, the material
Material first discharge specific capacity is 152.87mAh/g, and discharge capacity is 118.91mAh/g after 100 circle circulations, and capacity retention ratio is
77.79%, high rate performance such as Fig. 6, capacity attenuation is very fast under high current density.
Embodiment 6：
It weighs 0.0425g EDETATE SODIUM and is dissolved in 4mL deionized water, 1g NCA is added and forms suspension, weighs 0.0296g
Mg(NO3)2·6H2O is dissolved in 3mL deionized water and above-mentioned suspension is added dropwise；To EDTA and Mg2+After complexing, 0.01g is weighed
(NH4)2HPO4It is dissolved in 3mL deionized water and above-mentioned mixed liquor is added dropwise, be centrifugated after magnetic agitation 1h at room temperature；It will be upper
30min is ground after stating product drying, 450 DEG C of heat preservation 5h in Muffle furnace are placed in, up to 1%Mg after cooling3(PO4)2@NCA。
By 1%Mg3(PO4)2@NCA material, conductive agent acetylene black, binder PVDF in mass ratio 8：1：1 grinding half an hour,
Dropwise addition NMP (N-methyl pyrrolidones) is adjusted to paste and is coated uniformly on aluminium foil, roll-in punching after drying, and positive plate is made；With
Metal lithium sheet is cathode, using microporous polypropylene membrane as diaphragm, with the LiPF of 1mol/L6For electrolyte, it is assembled into glove box
CR2032 type battery.
Assembled battery is subjected to constant current charge-discharge test at room temperature, voltage range is 2.8~4.3V, and the material is first
Secondary specific discharge capacity is 151.07mAh/g, and discharge capacity is 104.21mAh/g after 100 circle circulations, and capacity retention ratio is
68.98%, high rate performance such as Fig. 6.
Embodiment 7：
It weighs 0.0850g EDETATE SODIUM and is dissolved in 4mL deionized water, 1g NCA is added and forms suspension, weighs 0.0591g
Mg(NO3)2·6H2O is dissolved in 3mL deionized water and above-mentioned suspension is added dropwise；To EDTA and Mg2+After complexing, weigh
0.0201g(NH4)2HPO4It is dissolved in 3mL deionized water and above-mentioned mixed liquor is added dropwise, centrifugation point after magnetic agitation 1h at room temperature
From；30min will be ground after the drying of above-mentioned product, is placed in 450 DEG C of heat preservation 5h in Muffle furnace.Up to 2%Mg after cooling3(PO4)2@
NCA。
By 2%Mg3(PO4)2@NCA material, conductive agent acetylene black, binder PVDF in mass ratio 8：1：1 grinding half an hour,
Dropwise addition NMP (N-methyl pyrrolidones) is adjusted to paste and is coated uniformly on aluminium foil, roll-in punching after drying, and positive plate is made；With
Metal lithium sheet is cathode, using microporous polypropylene membrane as diaphragm, with the LiPF of 1mol/L6For electrolyte, it is assembled into glove box
CR2032 type battery.
Assembled battery is subjected to constant current charge-discharge test at room temperature, voltage range is 2.8~4.3V, and the material is first
Secondary specific discharge capacity is 151.95mAh/g, and discharge capacity is 134.89mAh/g after 100 circle circulations, and capacity retention ratio is
88.77%, high rate performance such as Fig. 6, high rate capability is obviously improved.
Embodiment 8：
It weighs 0.2125g EDETATE SODIUM and is dissolved in 4mL deionized water, 1g NCA is added and forms suspension, weighs 0.1463g
Mg(NO3)2·6H2O is dissolved in 3mL deionized water and above-mentioned suspension is added dropwise.To EDTA and Mg2+After complexing, weigh
0.0502g(NH4)2HPO4It is dissolved in 3mL deionized water and above-mentioned mixed liquor is added dropwise, centrifugation point after magnetic agitation 1h at room temperature
From；30min will be ground after the drying of above-mentioned product, is placed in 450 DEG C of heat preservation 5h in Muffle furnace.Up to 5%Mg after cooling3(PO4)2@
NCA。
By 5%Mg3(PO4)2@NCA material, conductive agent acetylene black, binder PVDF in mass ratio 8：1：1 grinding half an hour,
Dropwise addition NMP (N-methyl pyrrolidones) is adjusted to paste and is coated uniformly on aluminium foil, roll-in punching after drying, and positive plate is made；With
Metal lithium sheet is cathode, using microporous polypropylene membrane as diaphragm, with the LiPF of 1mol/L6For electrolyte, it is assembled into glove box
CR2032 type battery.
Assembled battery is subjected to constant current charge-discharge test at room temperature, voltage range is 2.8~4.3V, and the material is first
Secondary specific discharge capacity is 142.44mAh/g, and discharge capacity is 99.80mAh/g after 100 circle circulations, and capacity retention ratio is
70.06%, high rate performance such as Fig. 6, high rate capability is slightly promoted.
Claims (9)
1. a kind of preparation method of Phosphate coating nickel cobalt aluminium tertiary cathode material, it is characterised in that：
It is to be coated with phosphate on the surface of the kernel, and in cladding process using nickel cobalt aluminium tertiary cathode material as kernel
Middle addition chelating agent, to promote Phosphate coating on nickel cobalt aluminium tertiary cathode material surface；
The general formula of the nickel cobalt aluminium tertiary cathode material is LiNi1-x-yCoxAlyO2, wherein 0 x≤0.2 <, 0 y≤0.05 <.
2. preparation method according to claim 1, it is characterised in that：
The phosphate is Ma(PO4)b, at least one of M Fe, Ni, Al, Mg, Zn, Co.
3. preparation method according to claim 1 or 2, it is characterised in that include the following steps：
Step 1：Using coprecipitation, nickel cobalt aluminium presoma is prepared under an inert atmosphere；
Step 2：Nickel cobalt aluminium presoma and lithium source made from step 1 are mixed and ground, the first mixture is obtained；
Step 3：The first mixture of gained is warming up to 450~500 in oxygen-supplying tube formula furnace with the heating rate of 2~5 DEG C/min
DEG C, keep the temperature 6h, then be warming up to 750~850 DEG C with the heating rate of 2~5 DEG C/min, be ground up, sieved after furnace cooling up to lithium from
Sub- battery tertiary cathode material LiNi1-x-yCoxAlyO2；
Step 4：The source M, phosphorus source and chelating agent are weighed, LiNi is added after the source M and chelating agent are dissolved with aqueous solvent1-x-yCoxAlyO2,
Then phosphorus source and magnetic agitation 1-5h is added dropwise, in 400~500 DEG C of 5~8h of heat preservation, i.e., centrifuge separation is subsequently placed in Muffle furnace
Obtain Phosphate coating tertiary cathode material.
4. preparation method according to claim 3, it is characterised in that：
In step 1, the nickel cobalt aluminium presoma is at least one of nickel cobalt aluminium hydroxide, nickel cobalt aluminium carbonate.
5. preparation method according to claim 3, it is characterised in that：
In step 1, the inert atmosphere is at least one of nitrogen, argon gas.
6. preparation method according to claim 3, it is characterised in that：
In step 2, the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium acetate.
7. preparation method according to claim 3, it is characterised in that：
In step 4, the source M is at least one of sulfate, nitrate；Phosphorus source is ammonium dihydrogen phosphate, phosphoric acid hydrogen two
At least one of ammonium, ammonium phosphate；The chelating agent is at least one of EDETATE SODIUM, PVP.
8. preparation method according to claim 3, it is characterised in that：
In step 4, the quality of phosphorus source is the 1~5% of tertiary cathode material quality；Mole of metal ion in chelating agent and the source M
Than being 1:1.
9. preparation method according to claim 3, it is characterised in that：
In terms of 1g tertiary cathode material quality, overall control≤10g of aqueous solvent in step 4.
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| CN109698346A (en) * | 2018-12-29 | 2019-04-30 | 蜂巢能源科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
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