CN108336344A - A kind of nickelic ternary anode material of lithium battery and preparation method of sodium ion doping - Google Patents
A kind of nickelic ternary anode material of lithium battery and preparation method of sodium ion doping Download PDFInfo
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- CN108336344A CN108336344A CN201810224086.4A CN201810224086A CN108336344A CN 108336344 A CN108336344 A CN 108336344A CN 201810224086 A CN201810224086 A CN 201810224086A CN 108336344 A CN108336344 A CN 108336344A
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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
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- 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
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Abstract
The present invention proposes a kind of nickelic ternary anode material of lithium battery and preparation method of sodium ion doping, 811 type NCM tertiary cathode presomas are prepared by coprecipitation, after being mixed with lithia with powdered sodium peroxide after presoma drying and grinding, the nickelic ternary anode material of lithium battery that sodium ion adulterates is obtained after pre-burning, sintering are carried out under oxygen-enriched environment.The present invention offer above method, which effectively overcomes, to be difficult to effectively control Ni in sintering process2+Deviate from embedded lithium layer from layer structure, causes structure change in desorption process to cause the defect that lithium ion capacity reduces, molten state is become in burn-in process by sodium peroxide and is infiltrated into inside presoma, by Ni2+It is oxidized to Ni3+, while lithium layer is occupied, expand interlayer structure, inhibits Ni2+It is migrated to lithium layer in sintering process, realizes the nickel lithium mixing for reducing nickelic NCM positive electrodes, while improving the mobility of lithium ion, improve the technique effect of cycle performance of battery.
Description
Technical field
The present invention relates to lithium ion field of material technology, and in particular to a kind of nickelic ternary lithium battery of sodium ion doping is just
Pole material and preparation method.
Background technology
Lithium ion battery and traditional accumulator are comparatively, not only energy higher, and discharge capability is stronger, and cycle life is more
It is long, and its energy storage efficiency can be more than 90%, and the above feature determines lithium ion battery in sides such as electric vehicle, storage power supplys
The great development prospect in face, lithium ion battery is high all the way with the development of electric vehicle, has become electric powered motor at present
Main source, type is various, with their own characteristics, is all difficult to be replaced by other power in following long period.With people
Requirement to lithium ion battery it is also higher and higher, exploitation high power capacity, the lithium battery of high-energy density are more and more important.
Cobalt nickel lithium manganate ternary material LiNi1-x-yCoxMyO2（Molar fraction >=0.6 of NCM, Ni) by feat of high power capacity, good
The advantages such as security performance, the scale application in power battery, but high nickel content brings structural instability and high temperature is swollen
The serious problem of gas.
The raw material of nickelic positive electrode is synthesized mainly based on hydroxide precursor, wherein Ni is with Ni2+Form exists.It burns
During knot, by high temperature and oxidizing atmosphere by Ni2+It is oxidized to Ni3+, however Ni2+It is transformed into Ni3+Even if energy barrier it is higher
Also complete oxidation, remaining Ni are difficult under pure oxygen atmosphere2+3b will be occupied so that cationic charge reduces, in order to keep electricity
Lotus balances, part Ni2+3a embedded lithium layer can be occupied and substitute part Li+, formation is non-metering to compare material.Improving temperature can promote
Make more Ni2+Oxidation, but the volatile quantity of lithium exponentially rises with the raising of temperature, leads to non-stoichiometric material shape
At.In addition, nickelic positive electrode structural instability at high temperature, it is active vertical to generate that there is no lithium ion deintercalations in cyclic process
Square rock salt phase, so as to cause material forthright reduction again.Due to being difficult to effectively control Ni in sintering process2+It is taken off from layer structure
Go out embedded lithium layer, causes the structure change in lithium ion capacity reduction and desorption process, therefore be directed to lithium ion cell positive material
The study on the modification of material has a very important significance.
Lithium ion battery anode material doped processing is one of current main method of modifying, and the effect of doping is mainly reflected in
Following two aspects：(1) to the influence of first charge discharge efficiency and cycle performance, doping can inhibit in charge and discharge process to a certain extent
Reversible transition；(2) doping can buffer the variation of removal lithium embedded sandwich, reduce material under Charging state with battery each group
/ reaction, so as to improve the cycle life and security performance of material.Different ions are adulterated, generated improvement
It is different.
As to disclose the cobalt magnesium based on high-nickel material codoping modified for Chinese invention patent application number 201710167988.4
The preparation method of ternary precursor and positive electrode, by nickel cobalt magnesium mixed solution, ammonium hydroxide and sodium hydroxide mixed solution, hydroxide
Sodium solution cocurrent is added in reaction kettle, after coprecipitation reaction, first obtains precursor powder, then precursor powder is mixed with lithium salts
Uniformly, it is calcined in tube furnace, is ground up, sieved to obtain nickelic tertiary cathode material.It is accounted in Li in the program by adulterating Mg
Position forms defect and vacancy, makes the reduction of insertion/deintercalation process middle impedance, but is still unavoidable from remaining in calcination process
Ni2+Generation and its substitute Li possibilities, improvement is limited.
Chinese invention patent application number 201510234496.3 discloses a kind of system of aluminium element doping tertiary cathode material
Preparation Method prepares aluminium by using coprecipitation and adulterates ternary anode material precursor, improves ternary anode material precursor
Physical and chemical performance LBO is used in combination to improve the bulk density and cycle performance of tertiary cathode material（Li2O-2B2O3）Surface coats
To aluminium doping tertiary cathode material LiNi 0.6Co0.15Mn0.05Al0.2O2It is modified, improves the property of aluminium doping tertiary cathode material
Energy.But the program needs to carry out surface cladding to aluminium doping ternary anode material precursor, complex disposal process influences to change
The factor of property effect is numerous.
Above by being carried out to nickelic ternary material, cobalt magnesium is co-doped with, cladding scheme to a certain extent may be used after aluminium doping treatment
To inhibit its structural instability, but it is still unavoidable from Ni remaining in calcination process2+Generation and its Li can
Energy property, improvement are limited.Therefore, it is necessary to propose a kind of simple preparation method, inhibit Ni2+To lithium layer in sintering process
Migration, reduces the nickel lithium mixing of nickelic tertiary cathode material, the mobility of lithium ion is improved, for following for nickelic lithium ion battery
Ring stability study has highly important practical significance.
Invention content
For being difficult to effectively control Ni in sintering process2+Deviate from embedded lithium layer from layer structure, causes desorption process
In structure change cause the defect that lithium ion capacity reduces, the present invention to propose a kind of nickelic ternary lithium battery of sodium ion doping
Positive electrode and preparation method inhibit Ni2+It is migrated to lithium layer in sintering process, the nickel lithium for reducing nickelic tertiary cathode material is mixed
Row, to improve layer structure stability, improves the cyclical stability of lithium ion battery.
To solve the above problems, the present invention uses following technical scheme：
The nickelic ternary anode material of lithium battery and preparation method of a kind of sodium ion doping, by sodium peroxide powder and lithia and
NCM presomas mix, and pre-burning, sintering are carried out under excess oxygen, obtains the nickelic ternary lithium battery anode material of sodium ion doping
Material, specific preparation process are as follows：
（1）Using nickel salt, cobalt salt, manganese salt, lithium salts and sodium peroxide as raw material, 0.8 part of nickel salt is weighed according to molar ratio, 0.1
Part cobalt salt, 0.1 part of manganese salt, 0.485 part of lithia and 0.015 part of sodium peroxide；
（2）The nickel salt, cobalt salt, manganese salt are separately added into appropriate acid solution, appropriate alkaline solution adjusting pH value, which is added, is
Between 10-12, NCM co-precipitation dispersion liquids are obtained under high velocity agitation, is handled using filtering and low temperature drying, obtains 811 types
NCM presomas；
（3）The 811 type NCM presomas are added in ball mill and are ground, are maintained the temperature between 60-120 DEG C in process of lapping,
Obtain the precursor powder that grain size is 10-150nm；
（4）The precursor powder is mixed with sodium peroxide powder and oxidation lithium powder by high-speed stirred, in oxygen-enriched environment
Under, pre-burning, sintering are carried out, the nickelic ternary anode material of lithium battery of sodium ion doping is obtained.
Preferably, the nickel salt is one kind in nickel chloride, nickelous carbonate, nickel nitrate, nickel hydroxide, nickelous bromide, nickel fluoride,
The cobalt salt is cobalt chloride, cobalt carbonate, cobalt nitrate, cobalt acid sodium, cobaltous bromide, one kind in cobaltous fluoride, the manganese salt be manganese chloride,
One kind in manganese carbonate, manganese nitrate, sodium manganate, manganous bromide, manganous fluoride.
Preferably, the acid solution is phosphoric acid solution, hydrochloric acid solution, salpeter solution, one kind in sulfuric acid solution or two
Kind or more combination, pH value 1-3.
Preferably, the alkaline solution is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, bicarbonate
The combination of one or more of potassium, ammonium hydroxide.
Preferably, step（2）Described in high-speed stirred speed be 200-800rpm.
Preferably, step（2）Described in low temperature drying refer to drying temperature be 50-70 DEG C, ambient pressure be 10-300 Pa.
Preferably, it is 30-50% that the oxygen-enriched environment, which is oxygen content, and controls carbon dioxide and other sour gas
Concentration be less than 0.2 ‰
Preferably, the calcined temperature is 450-550 DEG C, keeps the temperature 4-8h, and sintering temperature is 800-850 DEG C, is sintered 8-12h.
On the other hand a kind of nickelic ternary anode material of lithium battery of sodium ion doping is provided, be prepared by the above method
The nickelic ternary anode material of lithium battery Li of sodium ion doping0.97Na0.03Ni0.8Co0.1Mn0.1O2。
It prepares nickelic tertiary cathode material technology for existing and is difficult to effectively control Ni in sintering process2+From layer structure
Middle abjection is embedded in lithium layer, and the defect for causing the structure change in desorption process that lithium ion capacity is caused to reduce, the present invention proposes one
The nickelic ternary anode material of lithium battery and preparation method of kind sodium ion doping, 811 type NCM tri- are prepared by coprecipitation
First anode presoma, after being mixed with lithia with powdered sodium peroxide after presoma drying and grinding, under oxygen-enriched environment into
Row pre-burning, sintering, obtain the nickelic ternary anode material of lithium battery of sodium ion doping.The present invention is by sodium peroxide in pre-burning
Become molten state in journey to infiltrate into inside presoma, by Ni2+It is oxidized to Ni3+, while lithium layer is occupied, expand interlayer structure, inhibits
Ni2+It is migrated to lithium layer in sintering process, to improve layer structure stability, while the doping of sodium ion increases interlamellar spacing,
Be conducive to diffusion of the lithium ion in interlayer.
The present invention provides a kind of nickelic ternary anode material of lithium battery and preparation method of sodium ion doping, with the prior art
It compares, the feature and excellent effect protruded is：
1, the present invention becomes molten state in burn-in process by sodium peroxide and infiltrates into inside presoma, by Ni2+It is oxidized to Ni3 +, while lithium layer is occupied, expand interlayer structure, and then inhibit Ni2+It is migrated in the subsequent sintering process to lithium layer, reduces nickelic three
The nickel lithium mixing of first positive electrode, to improve layer structure stability, the doping increase interlamellar spacing of sodium ion when colluding, favorably
In lithium ion in the diffusion of interlayer, the mobility of lithium ion is improved, and then overcomes and is difficult to effectively control Ni in sintering process2+
Deviate from embedded lithium layer from layer structure, cause the structure change in desorption process, the defect for causing lithium ion capacity to reduce changes
The cyclical stability of kind lithium ion battery.
2, present invention process is simple and easy to control, and doping effect is good, without post-processing again, utilizes sodium ion of the present invention doping
Nickelic ternary lithium battery prepared by NCM positive electrodes has preferable chemical stability, the spy that capacity is high and cycle performance is excellent
Point.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）Using nickel chloride, cobalt chloride, manganese chloride, lithia and sodium peroxide as raw material, 0.8 part is weighed according to molar ratio
Nickel chloride, 0.1 part of cobalt chloride, 0.1 part of manganese chloride, 0.485 part of lithia and 0.015 part of sodium peroxide；
（2）It is that appropriate sodium hydroxide is added and adjusts in 3 phosphoric acid solutions that the nickel salt, cobalt salt, manganese salt, which are separately added into appropriate pH value,
PH value is 10, and setting mixing speed is 800rpm, NCM co-precipitation dispersion liquids is obtained under high velocity agitation, using filtering, processing
Condition is that drying temperature is 50 DEG C, and ambient pressure is low temperature drying under 300 Pa, obtains 811 type NCM presomas；
（3）The 811 type NCM presomas are added in ball mill and are ground, 60 DEG C are maintained the temperature in process of lapping, obtains grain size
For the precursor powder of 80nm；
（4）The precursor powder is mixed with sodium peroxide powder and oxidation lithium powder by high-speed stirred, in oxygen content
It is 35%, and controls under oxygen-enriched environment of the concentration less than 0.2 ‰ of carbon dioxide and other sour gas, carries out pre-burning, burns
Knot, calcined temperature are 450 DEG C, keep the temperature 8h, and sintering temperature is 850 DEG C, is sintered 12h, obtains the nickelic ternary lithium of sodium ion doping
Cell positive material Li0.97Na0.03Ni0.8Co0.1Mn0.1O2。
Embodiment 2
（1）Using nickel nitrate, cobalt nitrate, manganese nitrate, lithia and sodium peroxide as raw material, 0.8 part is weighed according to molar ratio
Nickel salt, 0.1 part of cobalt salt, 0.1 part of manganese salt, 0.485 part of lithia and 0.015 part of sodium peroxide；
（2）It is that appropriate alkaline solution carbonic acid is added in 3 hydrochloric acid solutions that the nickel salt, cobalt salt, manganese salt, which are separately added into appropriate pH value,
It is 11 that sodium, which adjusts pH value, and setting mixing speed is 600rpm, NCM co-precipitation dispersion liquids is obtained under high velocity agitation, using mistake
Filter, treatment conditions are that drying temperature is 55 DEG C, and ambient pressure is low temperature drying under 30Pa, obtains 811 type NCM presomas；
（3）The 811 type NCM presomas are added in ball mill and are ground, 80 DEG C are maintained the temperature in process of lapping, obtains grain size
For the precursor powder of 50nm；
（4）The precursor powder is mixed with sodium peroxide powder and oxidation lithium powder by high-speed stirred, in oxygen content
It is 50%, and controls under oxygen-enriched environment of the concentration less than 0.2 ‰ of carbon dioxide and other sour gas, carries out pre-burning, burns
Knot, calcined temperature are 550 DEG C, keep the temperature 4h, and sintering temperature is 800 DEG C, is sintered 2h, obtain the nickelic ternary lithium electricity of sodium ion doping
Pond positive electrode Li0.97Na0.03Ni0.8Co0.1Mn0.1O2。
Embodiment 3
（1）Using nickelous bromide, cobaltous bromide, manganous bromide, lithia and sodium peroxide as raw material, 0.8 part is weighed according to molar ratio
Nickel salt, 0.1 part of cobalt salt, 0.1 part of manganese salt, 0.485 part of lithia and 0.015 part of sodium peroxide；
（2）It is to be added in 3 sulfuric acid, hydrochloric acid and nitric acid mixed solution that the nickel salt, cobalt salt, manganese salt, which are separately added into appropriate pH value,
It is 12 that appropriate potassium hydroxide, which adjusts pH value, and setting mixing speed is 300rpm, obtains NCM co-precipitation dispersions under high velocity agitation
Liquid is that drying temperature is 55 DEG C using filtering, treatment conditions, and ambient pressure is low temperature drying under 180 Pa, obtains 811 types
NCM presomas；
（3）The 811 type NCM presomas are added in ball mill and are ground, 100 DEG C are maintained the temperature in process of lapping, obtains grain
Diameter is the precursor powder of 30nm；
（4）The precursor powder is mixed with sodium peroxide powder and oxidation lithium powder by high-speed stirred, in oxygen content
It is 35%, and controls under oxygen-enriched environment of the concentration less than 0.2 ‰ of carbon dioxide and other sour gas, carries out pre-burning, burns
Knot, calcined temperature are 500 DEG C, keep the temperature 6h, and sintering temperature is 820 DEG C, is sintered 10h, obtains the nickelic ternary lithium of sodium ion doping
Cell positive material Li0.97Na0.03Ni0.8Co0.1Mn0.1O2。
Embodiment 4
（1）Using nickelous carbonate, cobalt carbonate, manganese carbonate, lithia and sodium peroxide as raw material, 0.8 part is weighed according to molar ratio
Nickel salt, 0.1 part of cobalt salt, 0.1 part of manganese salt, 0.485 part of lithia and 0.015 part of sodium peroxide；
（2）It is 3 hydrochloric acid solutions that the nickel salt, cobalt salt, manganese salt, which are separately added into appropriate pH value, adds proper amount of sodium carbonate, carbonic acid
It is 11 that hydrogen sodium mixed liquor, which adjusts pH value, and setting mixing speed is 500rpm, obtains NCM co-precipitation dispersion liquids under high velocity agitation,
It is that drying temperature is 65 DEG C using filtering, treatment conditions, ambient pressure is low temperature drying under 200 Pa, before obtaining 811 type NCM
Drive body；
（3）The 811 type NCM presomas are added in ball mill and are ground, are maintained the temperature between 60-80 DEG C in process of lapping,
Obtain the precursor powder that grain size is 80nm；
（4）The precursor powder is mixed with sodium peroxide powder and oxidation lithium powder by high-speed stirred, in oxygen content
It is 45%, and controls under oxygen-enriched environment of the concentration less than 0.2 ‰ of carbon dioxide and other sour gas, carries out pre-burning, burns
Knot, calcined temperature are 520 DEG C, keep the temperature 5h, and sintering temperature is 810 DEG C, is sintered 12h, obtains the nickelic ternary lithium of sodium ion doping
Cell positive material Li0.97Na0.03Ni0.8Co0.1Mn0.1O2。
Embodiment 5
（1）Using nickel hydroxide, cobalt nitrate, sodium manganate, lithia and sodium peroxide as raw material, 0.8 is weighed according to molar ratio
Part nickel salt, 0.1 part of cobalt salt, 0.1 part of manganese salt, 0.485 part of lithia and 0.015 part of sodium peroxide；
（2）It is to be added in 3 hydrochloric acid solutions and salpeter solution mixed liquor that the nickel salt, cobalt salt, manganese salt, which are separately added into appropriate pH value,
It is 12 that appropriate alkaline solution potassium hydroxide, saleratus, ammonia water mixture, which adjust pH value, and setting mixing speed is 700rpm,
NCM co-precipitation dispersion liquids are obtained under high-speed stirred, are that drying temperature is 58 DEG C using filtering, treatment conditions, ambient pressure is
Low temperature drying under 200 Pa obtains 811 type NCM presomas；
（3）Will the 811 type NCM presomas be added ball mill in grind, maintained the temperature in process of lapping 100-120 DEG C it
Between, obtain the precursor powder that grain size is 150nm；
（4）The precursor powder is mixed with sodium peroxide powder and oxidation lithium powder by high-speed stirred, in oxygen content
It is 50%, and controls under oxygen-enriched environment of the concentration less than 0.2 ‰ of carbon dioxide and other sour gas, carries out pre-burning, burns
Knot, calcined temperature are 458 DEG C, keep the temperature 6h, and sintering temperature is 820 DEG C, is sintered 11h, obtains the nickelic ternary lithium of sodium ion doping
Cell positive material Li0.97Na0.03Ni0.8Co0.1Mn0.1O2。
Comparative example 1
（1）Using nickel hydroxide, cobalt nitrate, sodium manganate, lithia as raw material, 0.8 part of nickel salt is weighed according to molar ratio, 0.1
Part cobalt salt, 0.1 part of manganese salt, 0.5 part of lithia；
（2）It is to be added in 3 hydrochloric acid solutions and salpeter solution mixed liquor that the nickel salt, cobalt salt, manganese salt, which are separately added into appropriate pH value,
It is 12 that appropriate alkaline solution potassium hydroxide, saleratus, ammonia water mixture, which adjust pH value, and setting mixing speed is 700rpm,
NCM co-precipitation dispersion liquids are obtained under high-speed stirred, are that drying temperature is 58 DEG C using filtering, treatment conditions, ambient pressure is
Low temperature drying under 200 Pa obtains 811 type NCM presomas；
（3）Will the 811 type NCM presomas be added ball mill in grind, maintained the temperature in process of lapping 100-120 DEG C it
Between, obtain the precursor powder that grain size is 150nm；
（4）The precursor powder is mixed with oxidation lithium powder by high-speed stirred, is 50% in oxygen content, and control
Under oxygen-enriched environment of the concentration of carbon dioxide and other sour gas less than 0.2 ‰, pre-burning, sintering, calcined temperature 458 are carried out
DEG C, 6h is kept the temperature, sintering temperature is 820 DEG C, is sintered 11h, obtains the nickelic ternary anode material of lithium battery of sodium ion doping
LiNi0.8Co0.1Mn0.1O2。
Comparative example 2
By NiSO4, CoSO4, Mn (NO3) 3, AlCl3Ni in molar ratio：Co：Mn ：Al=8：1：0.7：0.3 ratio is dissolved in
In a certain amount of deionized water, it is configured to mixing salt solution, wherein metal ion total concentration is 1mol/L, is in addition prepared again
The NaOH solution of 2mol/L and the Na of 1mol/L2S2O8Solution.It is with the flow velocity of 20mL/min that 500mLNaOH is molten with metering pump
Liquid and 300mLNa2S2O8Solution is input in the metal salt mixed aqueous solution of 500mL simultaneously respectively to be reacted.Wait for lye
After being added completely into oxidizing agent solution, reaction kettle is sealed, normal pressure at 30 DEG C, continues to be stirred to react 5h, by above-mentioned coprecipitation reaction
Mixture is separated by solid-liquid separation, and is washed with deionized 3 times, filtrate is placed in baking oven, 12h is dried in vacuo at 100 DEG C,
Obtain dry aluminium doping ternary anode material precursor.
LiOH mixed grindings are added in above-mentioned drying object, that is, presoma, the addition of LiOH is Li：(Ni+Co+Mn+Al)
Molar ratio is 1.1：1, after grinding uniformly, the pre-burning 5h at 500 DEG C in air atmosphere for 24 hours then at 900 DEG C of sintering obtains surface
Cladding adulterates tertiary cathode material to aluminium：LiNi0.8Co0.1Mn0、07Al0.03O2。
By the obtained positive electrode of embodiment 1-5, comparative example 1-2 and acetylene black be made slurry agate grind alms bowl in grind
Kynoar is dissolved in 0. 7ml N-Methyl pyrrolidones by 30min, and the mixture added after grinding stirs 30 min, system
At slurry.Slurry is coated uniformly on the two-sided of 16 μm of aluminium foils, at 120 DEG C, dry 2h, later with the pressure pressure of 200 MPa
Positive plate is made in piece, the disk for being finally washed into a diameter of 8mm.Using metal lithium sheet as cathode, using conventional commercial electrolyte liquid and every
Film, is made cylindrical simulated battery test electrical property after positive/negative plate is assembled, room temperature constant current charge-discharge is carried out to battery is made
Test tests 0.1C, 1C first discharge specific capacity and cyclical stability using LAND battery test systems (CT2001A),
As shown in table 1.
Table 1:
The present invention becomes molten state in burn-in process by sodium peroxide and infiltrates into inside presoma, and Ni2+ is oxidized to Ni3
+, while lithium layer is occupied, and expand interlayer structure, Ni2+ is inhibited to be migrated to lithium layer in sintering process, it is steady to improve layer structure
It is qualitative.The doping of sodium ion increases interlamellar spacing simultaneously, is conducive to diffusion of the lithium ion in interlayer.Therefore, compared to not using sodium
The comparative example 1 of doping, conventional aluminium adulterate comparative example 2, and present invention reduces the nickel lithium mixings of nickelic NCM positive electrodes, simultaneously
The mobility for improving lithium ion, improves cyclical stability.
Claims (9)
1. a kind of preparation method of the nickelic ternary anode material of lithium battery of sodium ion doping, which is characterized in that by sodium peroxide
Powder is mixed with lithia and NCM presomas, and pre-burning, sintering are carried out under excess oxygen, obtains nickelic the three of sodium ion doping
First anode material of lithium battery, specific preparation process are as follows：
（1）Using nickel salt, cobalt salt, manganese salt, lithia and sodium peroxide as raw material, 0.8 part of nickel salt is weighed according to molar ratio,
0.1 part of cobalt salt, 0.1 part of manganese salt, 0.485 part of lithia and 0.015 part of sodium peroxide；
（2）The nickel salt, cobalt salt, manganese salt are separately added into appropriate acid solution, appropriate alkaline solution adjusting pH value, which is added, is
Between 10-12, NCM co-precipitation dispersion liquids are obtained under high velocity agitation, is handled using filtering and low temperature drying, obtains 811 types
NCM presomas；
（3）The 811 type NCM presomas are added in ball mill and are ground, are maintained the temperature between 60-120 DEG C in process of lapping,
Obtain the precursor powder that grain size is 10-150nm；
（4）The precursor powder is mixed with sodium peroxide powder and oxidation lithium powder by high-speed stirred, in oxygen-enriched environment
Under, pre-burning, sintering are carried out, the nickelic ternary anode material of lithium battery of sodium ion doping is obtained.
2. the nickelic ternary anode material of lithium battery and preparation method of a kind of sodium ion doping according to claim 1,
It is characterized in that, the nickel salt is one kind in nickel chloride, nickelous carbonate, nickel nitrate, nickelous bromide, nickel fluoride, and the cobalt salt is chlorination
One kind in cobalt, cobalt carbonate, cobalt nitrate, cobalt acid sodium, cobaltous bromide, cobaltous fluoride, the manganese salt be manganese chloride, manganese carbonate, manganese nitrate,
One kind in sodium manganate, manganous bromide, manganous fluoride.
3. the nickelic ternary anode material of lithium battery and preparation method of a kind of sodium ion doping according to claim 2,
It is characterized in that, the acid solution is one or more of phosphoric acid solution, hydrochloric acid solution, salpeter solution, sulfuric acid solution
Combination, pH value 1-3.
4. the nickelic ternary anode material of lithium battery and preparation method of a kind of sodium ion doping according to claim 1,
It is characterized in that, the alkaline solution is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, saleratus, ammonium hydroxide
One or more of combination.
5. the nickelic ternary anode material of lithium battery and preparation method of a kind of sodium ion doping according to claim 1,
It is characterized in that, step（2）Described in high-speed stirred speed be 200-800rpm.
6. the nickelic ternary anode material of lithium battery and preparation method of a kind of sodium ion doping according to claim 1,
It is characterized in that, step（2）Described in low temperature drying refer to drying temperature be 50-70 DEG C, ambient pressure be 10-300 Pa.
7. the nickelic ternary anode material of lithium battery and preparation method of a kind of sodium ion doping according to claim 1,
It is characterized in that, the oxygen-enriched environment is that oxygen content is 30-50%, and controls the concentration of carbon dioxide and other sour gas
Less than 0.2 ‰.
8. the nickelic ternary anode material of lithium battery and preparation method of a kind of sodium ion doping according to claim 1,
It is characterized in that, the calcined temperature is 450-550 DEG C, keeps the temperature 4-8h, and sintering temperature is 800-850 DEG C, is sintered 8-12h.
9. a kind of nickelic ternary anode material of lithium battery of sodium ion doping, which is characterized in that according to any one of claim 1-8
The nickelic ternary anode material of lithium battery Li of sodium ion doping is prepared in the method0.97Na0.03Ni0.8Co0.1Mn0.1O2。
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