CN109817919A - A kind of ternary cathode material of lithium ion battery and preparation method thereof of rubidium doping - Google Patents
A kind of ternary cathode material of lithium ion battery and preparation method thereof of rubidium doping Download PDFInfo
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- CN109817919A CN109817919A CN201910058227.4A CN201910058227A CN109817919A CN 109817919 A CN109817919 A CN 109817919A CN 201910058227 A CN201910058227 A CN 201910058227A CN 109817919 A CN109817919 A CN 109817919A
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Abstract
The present invention provides a kind of ternary cathode material of lithium ion batteries and preparation method thereof of rubidium doping.The ternary cathode material of lithium ion battery of the rubidium doping, which is characterized in that its chemical formula is RbxLi1-xNi0.6Co0.2Mn0.2O2, 0.005≤x≤0.02.The preparation method includes: to weigh to stir evenly in nickel oxide, cobalt oxide, manganese dioxide, lithium carbonate and rubidium carbonate addition deionized water, obtains uniform mixed liquor；By resulting mixed liquor ball milling, spray drying obtains ternary cathode material of lithium ion battery presoma powder；Briquetting processing is carried out, is calcined under oxygen atmosphere, the ternary cathode material of lithium ion battery of rubidium doping is obtained.The ternary cathode material of lithium ion battery that the present invention obtains, cationic mixing is low, and specific capacity is high, good rate capability and the simply suitable industrialized production of synthesis technology.
Description
Technical field
The invention belongs to lithium ion battery manufacturing field, the lithium ion battery tertiary cathode that specifically a kind of rubidium adulterates
Material and preparation method thereof.
Background technique
After the research and development of more than two decades, lithium ion battery has been widely used in our daily life now
In, such as portable electronic device mobile phone, laptop, video camera.Unquestionably, lithium ion battery we life,
Play very important role in production, will live irreplaceable a part as us.In addition, large-scale lithium ion battery
In big machinery as played and can not despise in terms of electric car, aerospace field, military field, network load
Effect；And minicell also has important application in this kind of microelectromechanicpositioning instrument such as miniature reconnaissance plane, micromotor.It is worth one
It is mentioned that, lithium ion battery applications are in Hyundai Motor, as hybrid vehicle, charged type hybrid power vehicle, pure electric vehicle
The preferred energy is the important guarantee for realizing energy sustainable development.
It is a kind of great development prospect with the cobalt nickel lithium manganate ternary material that nickel salt, cobalt salt, manganese salt are prepared as a raw material
Positive electrode.Ternary material combines LiCoO by the synergistic effect of Ni-Co-Mn2、LiNiO2、LiMnO2Three kinds of materials
Advantage: LiCoO2Preferable cycle performance, LiNiO2Higher specific capacity, LiMnO2Higher safety and low cost etc. are one
The very wide positive electrode of kind application prospect.
Ternary cathode material of lithium ion battery there are capacity attenuations very fast, the lower phenomenon of high rate performance, main cause
Be exactly structural instability, can be improved by adulterating some metal ions or nonmetallic ion not only in its lattice electronics and
Ionic conductivity can also improve the output power density of battery and the structural stability of material.Therefore by the way of doping
To improve structural stability, improve material electrochemical performance.
Summary of the invention
The object of the present invention is to provide a kind of anode material for lithium-ion batteries with good high rate performance and its preparation sides
Method.
In order to achieve the above object, the present invention provides a kind of ternary cathode material of lithium ion batteries of rubidium doping, special
Sign is, chemical formula RbxLi1-xNi0.6Co0.2Mn0.2O2, 0.005≤x≤0.02.
Preferably, the x=0.005,0.01,0.02.
The present invention also provides the preparation method of the ternary cathode material of lithium ion battery of above-mentioned rubidium doping, feature exists
In, comprising:
Step 1: weigh the nickel oxide of 90.5 parts by weight, the cobalt oxide of 30.2 parts by weight, 35.1 parts by weight manganese dioxide,
The lithium carbonate of 76.8-77.9 parts by weight and the rubidium carbonate of 1.1-4.6 parts by weight, which are added in the deionized water of 700-900 parts by weight, to be stirred
It mixes uniformly, obtains uniform mixed liquor；
Step 2: the resulting mixed liquor of step 1 is added to ball milling 30-120min in nanon ball-mill, take out slurry in
It is spray-dried at 160-180 DEG C, obtains ternary cathode material of lithium ion battery presoma powder；
Step 3: the resulting powder of step 2 being subjected to briquetting (2-6MPa) processing, is calcined under oxygen atmosphere, first
It is warming up to 400-550 DEG C and keeps the temperature 4-6h, then heat to 750-900 DEG C of heat preservation 8-12h, calcining terminates to adulterate to get to rubidium
Ternary cathode material of lithium ion battery RbxLi1-xNi0.6Co0.2Mn0.2O2,0.005≤x≤0.02。
Preferably, the chemical formula Rb of the ternary cathode material of lithium ion battery of rubidium dopingxLi1- xNi0.6Co0.2Mn0.2O2, x=0.005 is raw materials used as follows in parts by weight in step 1: lithium carbonate: 77.9 parts, carbonic acid
Rubidium: 1.1 parts, nickel oxide: 90.5 parts, cobalt oxide: 30.2 parts and manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: first
It is warming up to 400-550 DEG C and keeps the temperature 4-6h, then heat to 900 DEG C of heat preservation 8h, calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1- xNi0.6Co0.2Mn0.2O2, x=0.005 is as follows in parts by weight with raw material in step 1: lithium carbonate: 77.9 parts, rubidium carbonate:
1.1 parts, nickel oxide: 90.5 parts, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: heat up first
To 400-550 DEG C and 4-6h is kept the temperature, then heats to 850 DEG C of heat preservation 10h, calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1- xNi0.6Co0.2Mn0.2O2, x=0.005 is raw materials used as follows in parts by weight in step 1: lithium carbonate: 77.9 parts, carbonic acid
Rubidium: 1.1 parts, nickel oxide: 90.5 parts, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: rise first
Temperature is to 400-550 DEG C and keeps the temperature 4-6h, then heats to 750 DEG C of heat preservation 12h, calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1- xNi0.6Co0.2Mn0.2O2, x=0.01 is raw materials used as follows in parts by weight in step 1: lithium carbonate: 77.6 parts, carbonic acid
Rubidium: 2.3 parts, nickel oxide: 90.5 parts, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: rise first
Temperature is to 400-550 DEG C and keeps the temperature 4-6h, then heats to 900 DEG C of heat preservation 8h, calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1- xNi0.6Co0.2Mn0.2O2, x=0.01 is raw materials used as follows in parts by weight in step 1: lithium carbonate: 77.6 parts, carbonic acid
Rubidium: 2.3 parts, nickel oxide: 90.5 parts, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: rise first
Temperature is to 400-550 DEG C and keeps the temperature 4-6h, then heats to 850 DEG C of heat preservation 10h, calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1- xNi0.6Co0.2Mn0.2O2, x=0.01 is raw materials used as follows in parts by weight in step 1: lithium carbonate: 77.6 parts, carbonic acid
Rubidium: 2.3 parts, nickel oxide: 90.5 parts, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: rise first
Temperature is to 400-550 DEG C and keeps the temperature 4-6h, then heats to 750 DEG C of heat preservation 12h, calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1- xNi0.6Co0.2Mn0.2O2, x=0.02 is raw materials used as follows in parts by weight in step 1: lithium carbonate: 76.8 parts, carbonic acid
Rubidium: 4.6 parts, nickel oxide: 90.5 parts, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: rise first
Temperature is to 400-550 DEG C and keeps the temperature 4-6h, then heats to 900 DEG C of heat preservation 8h, calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1- xNi0.6Co0.2Mn0.2O2, x=0.02 is raw materials used as follows in parts by weight in step 1: lithium carbonate: 76.8 parts, carbonic acid
Rubidium: 4.3 parts, nickel oxide: 90.5 parts, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: rise first
Temperature is to 400-550 DEG C and keeps the temperature 4-6h, then heats to 850 DEG C of heat preservation 10h, calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1- xNi0.6Co0.2Mn0.2O2, x=0.02 is raw materials used as follows in parts by weight in step 1: lithium carbonate: 76.8 parts, carbonic acid
Rubidium: 4.3 parts, nickel oxide: 90.5 parts, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: rise first
Temperature is to 400-550 DEG C and keeps the temperature 4-6h, then heats to 750 DEG C of heat preservation 12h, calcining terminates.
The present invention first sequentially adds lithium carbonate, rubidium carbonate, nickel oxide, cobalt oxide, manganese dioxide in deionized water, mixes
Close uniformly after pour into nanon ball-mill grinding 30-120min obtain suspended matter slurry, be then spray-dried, after briquetting
Ternary cathode material of lithium ion battery is obtained after 750-900 DEG C of calcining 8-12h under oxygen atmosphere.
A kind of ternary cathode material of lithium ion battery of rubidium that the present invention obtains doping, primary particle size 200-400nm it
Between, tiny partial size is conducive to shorten the migration distance of lithium ion so that lithium ion diffusional resistance is smaller, promoted high rate performance and
Electrochemical stability.
The present invention is combined using nano ball grinding method with high temperature solid-state method, and simple production process is reliable, and cost is relatively low, is suitble to
Industrialized production.Raw material uses lithium carbonate and other metal oxides, does not generate polluted gas and waste water in production process, environmental protection
It is pollution-free.We carry out briquetting before calcination simultaneously, and the activity for improving reaction raw materials obtains lithium nickel mixing problem obviously
Improve.
The initial discharge specific capacity of rubidium doped lithium ion battery tertiary cathode material of the invention is 192.4mAh/g (0.1C
Under multiplying power), capacity boost is fairly obvious, while cationic mixing has obtained good control R value (003/104) and has been greater than 1.4, right
High rate performance promotion has significant help.
The present invention, compared with the existing technology, technological progress are significant.The lithium ion battery ternary that the present invention obtains
Positive electrode, cationic mixing is low, and specific capacity is high, good rate capability and the simply suitable industrialized production of synthesis technology.
Detailed description of the invention
The XRD spectrum of the ternary cathode material of lithium ion battery of 1 gained rubidium of Fig. 1 example doping；
The XRD refine map of the ternary cathode material of lithium ion battery of 1 gained rubidium of Fig. 2 example doping；
The SEM spectrum of the ternary cathode material of lithium ion battery of 1 gained rubidium of Fig. 3 example doping；
The charging and discharging curve map of the ternary cathode material of lithium ion battery of 1 gained rubidium of Fig. 4 example doping；
The high rate performance map of the ternary cathode material of lithium ion battery of 1 gained rubidium of Fig. 5 example doping；
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of preparation method of the ternary cathode material of lithium ion battery of rubidium doping, it is raw materials used in preparation process, by weight
Number is measured to calculate, comprising:
Lithium carbonate: 77.9 parts；
Rubidium carbonate: 1.1 parts；
Nickel oxide: 90.5 parts；
Cobalt oxide: 30.2 parts；
Manganese dioxide: 35.1 parts；
Its preparation process specifically comprises the following steps:
1) nickel oxide of 90.5 parts by weight, the cobalt oxide of 30.2 parts by weight, the manganese dioxide of 35.1 parts by weight, 77.9 are weighed
The lithium carbonate of parts by weight, 1.1 parts by weight rubidium carbonate be added in the deionized water of 800 parts by weight and stir evenly, obtain uniform
Mixed liquor.
2) mixed liquor obtained by step 1) is added to ball milling 1h in nanon ball-mill, takes out slurry and is sprayed at 170 DEG C
Mist is dry, obtains ternary cathode material of lithium ion battery presoma powder.
3) powder obtained by step 2) is subjected to briquetting processing, pressure 4MPa is calcined under oxygen atmosphere, risen first
Temperature is to 450 DEG C and keeps the temperature 5h, then heats to 900 DEG C of heat preservation 8h, and calcining terminates, and is adulterated by 300 mesh screens to rubidium
Ternary cathode material of lithium ion battery.
Using X-ray diffractometer (XRD, Rigaku Rigaku) to above-mentioned made ternary cathode material of lithium ion battery
It carries out object mutually to detect, object phase testing result is as shown in Figure 1.All diffraction maximums match with standard card and impurity do not occur
Peak, and R value (003/004) is 1.41, and it is obvious to divide peak, illustrate to obtain lithium nickel mixing using the above method few, crystallizes
Good layer structure.Diffracting spectrum after software (EXPGUI) refine (Fig. 2) is confirmed as R3-M space group, and refine result
Display Rb is that x=0.0049 meets theory expectation in Li occupy-place degree, that is, demonstrates Rb0.005Li0.995Ni0.6Co0.2Mn0.2O2。
As can be seen from Figure 3 for primary particle size between 200-400nm, pattern is uniform.
By the 0.8g lithium ion tertiary cathode material, 0.1g conductive carbon powder, 0.1g organic binder Kynoar of acquisition
(PVDF) 8:1:1 in mass ratio after mixing, is added 0.05mL nmp solvent, viscous syrup is sufficiently stirred into, uniformly coats
In aluminium foil surface, air blast drying is placed on the dry 8h of 120 DEG C of vacuum ovens, obtains positive plate after multiple roll-in.
Use the chemical property for the tertiary cathode material that the assessment of 2016 type half-cells obtains.By the good battery pole piece of roll-in
It strikes out the disk of diameter 12mm, after its quality of precise, tertiary cathode material in pole piece is calculated according to formula composition
Quality, the diaphragm diameter used are 19mm, and the cathode lithium piece diameter used is 15mm, are assembled into German Braun glove box
Button cell can be tested.
By above-mentioned button cell, electrochemical property test is carried out: as shown in figure 4, synthesized lithium ion battery tertiary cathode
First circle charging capacity of the material at 0.1C reaches 231.6mAh/g, and first circle specific discharge capacity reaches 192.4mAh/g, coulomb effect
Rate is 83.07%.It is illustrated in figure 5 the ternary cathode material of lithium ion battery high rate performance figure of synthesis, it can be seen that in 0.2C
Under reached the specific capacity of 176.7mAh/g, and performance is sufficiently stable under same multiplying power.Test result surface resulting materials tool
There is good chemical property that there is commercial application value.
Embodiment 2
A kind of preparation method of the ternary cathode material of lithium ion battery of rubidium doping, it is raw materials used in preparation process, by weight
It is as follows to measure number calculating:
Lithium carbonate: 77.9 parts
Rubidium carbonate: 1.1 parts
Nickel oxide: 90.5 parts
Cobalt oxide: 30.2 parts
Manganese dioxide: 35.1 parts
Its preparation process specifically comprises the following steps:
1) nickel oxide of 90.5 parts by weight, the cobalt oxide of 30.2 parts by weight, the manganese dioxide of 35.1 parts by weight, 77.9 are weighed
The lithium carbonate of parts by weight, 1.1 parts by weight rubidium carbonate be added in the deionized water of 800 parts by weight and stir evenly, obtain uniform
Mixed liquor.
2) mixed liquor obtained by step 1) is added to ball milling 1h in nanon ball-mill, takes out slurry and is sprayed at 170 DEG C
Mist is dry, obtains ternary cathode material of lithium ion battery presoma powder.
3) powder obtained by step 2) is subjected to briquetting processing, pressure 4MPa is calcined under oxygen atmosphere, risen first
Temperature is to 450 DEG C and keeps the temperature 5h, then heats to 850 DEG C of heat preservation 10h, and calcining terminates, and is adulterated by 300 mesh screens to get to rubidium
Ternary cathode material of lithium ion battery.
Using X-ray diffractometer (XRD, Rigaku Rigaku) to above-mentioned made ternary cathode material of lithium ion battery
Object is carried out mutually to detect.All diffraction maximums match with standard card and impurity peaks do not occur, and R value (003/004) is
1.40, and it is obvious to divide peak, illustrate to use the above method few, the layer structure of well-crystallized that obtains lithium nickel mixing.Diffraction
Map is confirmed as R3-M space group after software (EXPGUI) refine, and Rb in Li occupy-place degree is x as the result is shown for refine
=0.0051 meets theory expectation, that is, demonstrates Rb0.005Li0.995Ni0.6Co0.2Mn0.2O2.The material primary particle size is in 200-
Between 400nm, pattern is uniform.
Embodiment 3
A kind of preparation method of the ternary cathode material of lithium ion battery of rubidium doping, it is raw materials used in preparation process, by weight
It is as follows to measure number calculating:
Lithium carbonate: 77.9 parts
Rubidium carbonate: 1.1 parts
Nickel oxide: 90.5 parts
Cobalt oxide: 30.2 parts
Manganese dioxide: 35.1 parts
Its preparation process specifically comprises the following steps:
1) nickel oxide of 90.5 parts by weight, the cobalt oxide of 30.2 parts by weight, the manganese dioxide of 35.1 parts by weight, 77.9 are weighed
The lithium carbonate of parts by weight, 1.1 parts by weight rubidium carbonate be added in the deionized water of 800 parts by weight and stir evenly, obtain uniform
Mixed liquor.
2) mixed liquor obtained by step 1) is added to ball milling 1h in nanon ball-mill, takes out slurry and is sprayed at 170 DEG C
Mist is dry, obtains ternary cathode material of lithium ion battery presoma powder.
3) powder obtained by step 2) is subjected to briquetting processing, pressure 4MPa is calcined under oxygen atmosphere, risen first
Temperature is to 450 DEG C and keeps the temperature 5h, then heats to 750 DEG C of heat preservation 12h, and calcining terminates, and is adulterated by 300 mesh screens to get to rubidium
Ternary cathode material of lithium ion battery.
Using X-ray diffractometer (XRD, Rigaku Rigaku) to above-mentioned made ternary cathode material of lithium ion battery
Object is carried out mutually to detect.All diffraction maximums match with standard card and impurity peaks do not occur, and R value (003/004) is
1.37, and it is obvious to divide peak, illustrate to use the above method few, the layer structure of well-crystallized that obtains lithium nickel mixing.Diffraction
Map is confirmed as R3-M space group after software (EXPGUI) refine, and Rb in Li occupy-place degree is x as the result is shown for refine
=0.0048 meets theory expectation, that is, demonstrates Rb0.005Li0.995Ni0.6Co0.2Mn0.2O2.The material primary particle size is in 200-
Between 400nm, pattern is uniform.
Embodiment 4
A kind of preparation method of the ternary cathode material of lithium ion battery of rubidium doping, it is raw materials used in preparation process, by weight
It is as follows to measure number calculating:
Lithium carbonate: 77.6 parts
Rubidium carbonate: 2.3 parts
Nickel oxide: 90.5 parts
Cobalt oxide: 30.2 parts
Manganese dioxide: 35.1 parts
Its preparation process specifically comprises the following steps:
1) nickel oxide of 90.5 parts by weight, the cobalt oxide of 30.2 parts by weight, the manganese dioxide of 35.1 parts by weight, 77.6 are weighed
The lithium carbonate of parts by weight, 2.3 parts by weight rubidium carbonate be added in the deionized water of 800 parts by weight and stir evenly, obtain uniform
Mixed liquor.
2) mixed liquor obtained by step 1) is added to ball milling 1h in nanon ball-mill, takes out slurry and is sprayed at 170 DEG C
Mist is dry, obtains ternary cathode material of lithium ion battery presoma powder.
3) powder obtained by step 2) is subjected to briquetting processing, pressure 4MPa is calcined under oxygen atmosphere, risen first
Temperature is to 450 DEG C and keeps the temperature 5h, then heats to 900 DEG C of heat preservation 8h, and calcining terminates, and is adulterated by 300 mesh screens to rubidium
Ternary cathode material of lithium ion battery.
Using X-ray diffractometer (XRD, Rigaku Rigaku) to above-mentioned made ternary cathode material of lithium ion battery
Object is carried out mutually to detect.All diffraction maximums match with standard card and impurity peaks do not occur, and R value (003/004) is
1.40, and it is obvious to divide peak, illustrate to use the above method few, the layer structure of well-crystallized that obtains lithium nickel mixing.Diffraction
Map is confirmed as R3-M space group after software (EXPGUI) refine, and Rb in Li occupy-place degree is x as the result is shown for refine
=0.0099 meets theory expectation, that is, demonstrates Rb0.01Li0.99Ni0.6Co0.2Mn0.2O2.The material primary particle size is in 200-
Between 400nm, pattern is uniform.
Embodiment 5
A kind of preparation method of the ternary cathode material of lithium ion battery of rubidium doping, it is raw materials used in preparation process, by weight
It is as follows to measure number calculating:
Lithium carbonate: 77.6 parts
Rubidium carbonate: 2.3 parts
Nickel oxide: 90.5 parts
Cobalt oxide: 30.2 parts
Manganese dioxide: 35.1 parts
Its preparation process specifically comprises the following steps:
1) nickel oxide of 90.5 parts by weight, the cobalt oxide of 30.2 parts by weight, the manganese dioxide of 35.1 parts by weight, 77.6 are weighed
The lithium carbonate of parts by weight, 2.3 parts by weight rubidium carbonate be added in the deionized water of 800 parts by weight and stir evenly, obtain uniform
Mixed liquor.
2) mixed liquor obtained by step 1) is added to ball milling 1h in nanon ball-mill, takes out slurry and is sprayed at 170 DEG C
Mist is dry, obtains ternary cathode material of lithium ion battery presoma powder.
3) powder obtained by step 2) is subjected to briquetting processing, pressure 4MPa is calcined under oxygen atmosphere, risen first
Temperature is to 450 DEG C and keeps the temperature 5h, then heats to 850 DEG C of heat preservation 10h, and calcining terminates, and is adulterated by 300 mesh screens to get to rubidium
Ternary cathode material of lithium ion battery.
Using X-ray diffractometer (XRD, Rigaku Rigaku) to above-mentioned made ternary cathode material of lithium ion battery
Object is carried out mutually to detect.All diffraction maximums match with standard card and impurity peaks do not occur, and R value (003/004) is
1.42, and it is obvious to divide peak, illustrate to use the above method few, the layer structure of well-crystallized that obtains lithium nickel mixing.Diffraction
Map is confirmed as R3-M space group after software (EXPGUI) refine, and Rb in Li occupy-place degree is x as the result is shown for refine
=0.011 meets theory expectation, that is, demonstrates Rb0.01Li0.99Ni0.6Co0.2Mn0.2O2.The material primary particle size is in 200-
Between 400nm, pattern is uniform.
Embodiment 6
A kind of preparation method of the ternary cathode material of lithium ion battery of rubidium doping, it is raw materials used in preparation process, by weight
It is as follows to measure number calculating:
Lithium carbonate: 77.6 parts
Rubidium carbonate: 2.3 parts
Nickel oxide: 90.5 parts
Cobalt oxide: 30.2 parts
Manganese dioxide: 35.1 parts
Its preparation process specifically comprises the following steps:
1) nickel oxide of 90.5 parts by weight, the cobalt oxide of 30.2 parts by weight, the manganese dioxide of 35.1 parts by weight, 77.6 are weighed
The lithium carbonate of parts by weight, 2.3 parts by weight rubidium carbonate be added in the deionized water of 800 parts by weight and stir evenly, obtain uniform
Mixed liquor.
2) mixed liquor obtained by step 1) is added to ball milling 1h in nanon ball-mill, takes out slurry and is sprayed at 170 DEG C
Mist is dry, obtains ternary cathode material of lithium ion battery presoma powder.
3) powder obtained by step 2) is subjected to briquetting processing, pressure 4MPa is calcined under oxygen atmosphere, risen first
Temperature is to 450 DEG C and keeps the temperature 5h, then heats to 750 DEG C of heat preservation 12h, and calcining terminates, and is adulterated by 300 mesh screens to get to rubidium
Ternary cathode material of lithium ion battery.
Using X-ray diffractometer (XRD, Rigaku Rigaku) to above-mentioned made ternary cathode material of lithium ion battery
Object is carried out mutually to detect.All diffraction maximums match with standard card and impurity peaks do not occur, and R value (003/004) is
1.39, and it is obvious to divide peak, illustrate to use the above method few, the layer structure of well-crystallized that obtains lithium nickel mixing.Diffraction
Map is confirmed as R3-M space group after software (EXPGUI) refine, and Rb in Li occupy-place degree is x as the result is shown for refine
=0.0097 meets theory expectation, that is, demonstrates Rb0.01Li0.99Ni0.6Co0.2Mn0.2O2.The material primary particle size is in 200-
Between 400nm, pattern is uniform.
Embodiment 7
A kind of preparation method of the ternary cathode material of lithium ion battery of rubidium doping, it is raw materials used in preparation process, by weight
It is as follows to measure number calculating:
Lithium carbonate: 76.8 parts
Rubidium carbonate: 4.6 parts
Nickel oxide: 90.5 parts
Cobalt oxide: 30.2 parts
Manganese dioxide: 35.1 parts
Its preparation process specifically comprises the following steps:
1) nickel oxide of 90.5 parts by weight, the cobalt oxide of 30.2 parts by weight, the manganese dioxide of 35.1 parts by weight, 76.8 are weighed
The lithium carbonate of parts by weight, 4.6 parts by weight rubidium carbonate be added in the deionized water of 800 parts by weight and stir evenly, obtain uniform
Mixed liquor.
2) mixed liquor obtained by step 1) is added to ball milling 1h in nanon ball-mill, takes out slurry and is sprayed at 170 DEG C
Mist is dry, obtains ternary cathode material of lithium ion battery presoma powder.
3) powder obtained by step 2) is subjected to briquetting processing, pressure 4MPa is calcined under oxygen atmosphere, risen first
Temperature is to 450 DEG C and keeps the temperature 5h, then heats to 900 DEG C of heat preservation 8h, and calcining terminates, and is adulterated by 300 mesh screens to rubidium
Ternary cathode material of lithium ion battery.
Using X-ray diffractometer (XRD, Rigaku Rigaku) to above-mentioned made ternary cathode material of lithium ion battery
Object is carried out mutually to detect.All diffraction maximums match with standard card and impurity peaks do not occur, and R value (003/004) is
1.38, and it is obvious to divide peak, illustrate to use the above method few, the layer structure of well-crystallized that obtains lithium nickel mixing.Diffraction
Map is confirmed as R3-M space group after software (EXPGUI) refine, and Rb in Li occupy-place degree is x as the result is shown for refine
=0.021 meets theory expectation, that is, demonstrates Rb0.02Li0.98Ni0.6Co0.2Mn0.2O2.The material primary particle size is in 200-
Between 400nm, pattern is uniform.
Embodiment 8
A kind of preparation method of the ternary cathode material of lithium ion battery of rubidium doping, it is raw materials used in preparation process, by weight
It is as follows to measure number calculating:
Lithium carbonate: 76.8 parts
Rubidium carbonate: 4.6 parts
Nickel oxide: 90.5 parts
Cobalt oxide: 30.2 parts
Manganese dioxide: 35.1 parts
Its preparation process specifically comprises the following steps:
1) nickel oxide of 90.5 parts by weight, the cobalt oxide of 30.2 parts by weight, the manganese dioxide of 35.1 parts by weight, 76.8 are weighed
The lithium carbonate of parts by weight, 4.6 parts by weight rubidium carbonate be added in the deionized water of 800 parts by weight and stir evenly, obtain uniform
Mixed liquor.
2) mixed liquor obtained by step 1) is added to ball milling 1h in nanon ball-mill, takes out slurry and is sprayed at 170 DEG C
Mist is dry, obtains ternary cathode material of lithium ion battery presoma powder.
3) powder obtained by step 2) is subjected to briquetting processing, pressure 4MPa is calcined under oxygen atmosphere, risen first
Temperature is to 450 DEG C and keeps the temperature 5h, then heats to 850 DEG C of heat preservation 10h, and calcining terminates, and is adulterated by 300 mesh screens to get to rubidium
Ternary cathode material of lithium ion battery.
Using X-ray diffractometer (XRD, Rigaku Rigaku) to above-mentioned made ternary cathode material of lithium ion battery
Object is carried out mutually to detect.All diffraction maximums match with standard card and impurity peaks do not occur, and R value (003/004) is
1.42, and it is obvious to divide peak, illustrate to use the above method few, the layer structure of well-crystallized that obtains lithium nickel mixing.Diffraction
Map is confirmed as R3-M space group after software (EXPGUI) refine, and Rb in Li occupy-place degree is x as the result is shown for refine
=0.019 meets theory expectation, that is, demonstrates Rb0.02Li0.98Ni0.6Co0.2Mn0.2O2.The material primary particle size is in 200-
Between 400nm, pattern is uniform.
Embodiment 9
A kind of preparation method of the ternary cathode material of lithium ion battery of rubidium doping, it is raw materials used in preparation process, by weight
It is as follows to measure number calculating:
Lithium carbonate: 76.8 parts
Rubidium carbonate: 4.6 parts
Nickel oxide: 90.5 parts
Cobalt oxide: 30.2 parts
Manganese dioxide: 35.1 parts
Its preparation process specifically comprises the following steps:
1) nickel oxide of 90.5 parts by weight, the cobalt oxide of 30.2 parts by weight, the manganese dioxide of 35.1 parts by weight, 76.8 are weighed
The lithium carbonate of parts by weight, 4.6 parts by weight rubidium carbonate be added in the deionized water of 800 parts by weight and stir evenly, obtain uniform
Mixed liquor.
2) mixed liquor obtained by step 1) is added to ball milling 1h in nanon ball-mill, takes out slurry and is sprayed at 170 DEG C
Mist is dry, obtains ternary cathode material of lithium ion battery presoma powder.
3) powder obtained by step 2) is subjected to briquetting processing, pressure 4MPa is calcined under oxygen atmosphere, risen first
Temperature is to 450 DEG C and keeps the temperature 5h, then heats to 750 DEG C of heat preservation 12h, and calcining terminates, and is adulterated by 300 mesh screens to get to rubidium
Ternary cathode material of lithium ion battery.
Using X-ray diffractometer (XRD, Rigaku Rigaku) to above-mentioned made ternary cathode material of lithium ion battery
Object is carried out mutually to detect.All diffraction maximums match with standard card and impurity peaks do not occur, and R value (003/004) is
1.41, and it is obvious to divide peak, illustrate to use the above method few, the layer structure of well-crystallized that obtains lithium nickel mixing.Diffraction
Map is confirmed as R3-M space group after software (EXPGUI) refine, and Rb in Li occupy-place degree is x as the result is shown for refine
=0.021 meets theory expectation, that is, demonstrates Rb0.02Li0.98Ni0.6Co0.2Mn0.2O2.The material primary particle size is in 200-
Between 400nm, pattern is uniform.
Claims (4)
1. a kind of ternary cathode material of lithium ion battery of rubidium doping, which is characterized in that its chemical formula is RbxLi1-
xNi0.6Co0.2Mn0.2O2, 0.005≤x≤0.02.
2. the ternary cathode material of lithium ion battery of rubidium doping as described in claim 1, which is characterized in that the x=
0.005、0.01、0.02。
3. the preparation method of the ternary cathode material of lithium ion battery of rubidium doping of any of claims 1 or 2, which is characterized in that
Include:
Step 1: weigh the nickel oxide of 90.5 parts by weight, the cobalt oxide of 30.2 parts by weight, 35.1 parts by weight manganese dioxide,
The lithium carbonate of 76.8-77.9 parts by weight and the rubidium carbonate of 1.1-4.6 parts by weight, which are added in the deionized water of 700-900 parts by weight, to be stirred
It mixes uniformly, obtains uniform mixed liquor；
Step 2: the resulting mixed liquor of step 1 being added to ball milling 30-120min in nanon ball-mill, takes out slurry in 160-
It is spray-dried at 180 DEG C, obtains ternary cathode material of lithium ion battery presoma powder；
Step 3: the resulting powder of step 2 being subjected to briquetting processing, is calcined under oxygen atmosphere, is warming up to 400- first
550 DEG C and 4-6h is kept the temperature, then heat to 750-900 DEG C of heat preservation 8-12h, calcining terminates to get to the lithium-ion electric of rubidium doping
Pond tertiary cathode material RbxLi1-xNi0.6Co0.2Mn0.2O2,0.005≤x≤0.02。
4. the preparation method of the ternary cathode material of lithium ion battery of rubidium doping as claimed in claim 3, which is characterized in that institute
The chemical formula Rb of the ternary cathode material of lithium ion battery for the rubidium doping statedxLi1-xNi0.6Co0.2Mn0.2O2, x=0.005, step 1
In it is raw materials used as follows in parts by weight: lithium carbonate: 77.9 parts, rubidium carbonate: 1.1 parts, nickel oxide: 90.5 parts, cobalt oxide:
30.2 parts and manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: be warming up to 400-550 DEG C first and keep the temperature 4-6h, then
900 DEG C of heat preservation 8h are warming up to, calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1-xNi0.6Co0.2Mn0.2O2, x=
0.005, raw materials used as follows in parts by weight in step 1: lithium carbonate: 77.9 parts, rubidium carbonate: 1.1 parts, nickel oxide:
90.5 parts, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: be warming up to 400-550 DEG C first simultaneously
4-6h is kept the temperature, then heats to 850 DEG C of heat preservation 10h, calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1-xNi0.6Co0.2Mn0.2O2, x=
0.005, raw materials used as follows in parts by weight in step 1: lithium carbonate: 77.9 parts, rubidium carbonate: 1.1 parts, nickel oxide:
90.5 parts, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: be warming up to 400-550 DEG C first simultaneously
4-6h is kept the temperature, then heats to 750 DEG C of heat preservation 12h, calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1-xNi0.6Co0.2Mn0.2O2, x=
0.01, raw materials used as follows in parts by weight in step 1: lithium carbonate: 77.6 parts, rubidium carbonate: 2.3 parts, nickel oxide: 90.5
Part, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: be warming up to 400-550 DEG C first and keep the temperature
4-6h, then heats to 900 DEG C of heat preservation 8h, and calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1-xNi0.6Co0.2Mn0.2O2, x=
0.01, raw materials used as follows in parts by weight in step 1: lithium carbonate: 77.6 parts, rubidium carbonate: 2.3 parts, nickel oxide: 90.5
Part, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: be warming up to 400-550 DEG C first and keep the temperature
4-6h, then heats to 850 DEG C of heat preservation 10h, and calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1-xNi0.6Co0.2Mn0.2O2, x=
0.01, raw materials used as follows in parts by weight in step 1: lithium carbonate: 77.6 parts, rubidium carbonate: 2.3 parts, nickel oxide: 90.5
Part, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: be warming up to 400-550 DEG C first and keep the temperature
4-6h, then heats to 750 DEG C of heat preservation 12h, and calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1-xNi0.6Co0.2Mn0.2O2, x=
0.02, raw materials used as follows in parts by weight in step 1: lithium carbonate: 76.8 parts, rubidium carbonate: 4.6 parts, nickel oxide: 90.5
Part, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: be warming up to 400-550 DEG C first and keep the temperature
4-6h, then heats to 900 DEG C of heat preservation 8h, and calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1-xNi0.6Co0.2Mn0.2O2, x=
0.02, raw materials used as follows in parts by weight in step 1: lithium carbonate: 76.8 parts, rubidium carbonate: 4.3 parts, nickel oxide: 90.5
Part, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: be warming up to 400-550 DEG C first and keep the temperature
4-6h, then heats to 850 DEG C of heat preservation 10h, and calcining terminates；
Alternatively, the chemical formula Rb for the ternary cathode material of lithium ion battery that the rubidium adulteratesxLi1-xNi0.6Co0.2Mn0.2O2, x=
0.02, raw materials used as follows in parts by weight in step 1: lithium carbonate: 76.8 parts, rubidium carbonate: 4.3 parts, nickel oxide: 90.5
Part, cobalt oxide: 30.2 parts, manganese dioxide: 35.1 parts, calcination process in step 3 are as follows: be warming up to 400-550 DEG C first and keep the temperature
4-6h, then heats to 750 DEG C of heat preservation 12h, and calcining terminates.
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| CN111653763A (en) * | 2020-05-26 | 2020-09-11 | 上海应用技术大学 | Ternary lithium ion battery anode material and preparation method thereof |
| CN111952566A (en) * | 2020-08-18 | 2020-11-17 | 光鼎铷业(广州)集团有限公司 | Rubidium-doped high-rate lithium battery positive electrode material and preparation method thereof |
| CN111952585A (en) * | 2020-08-18 | 2020-11-17 | 光鼎铷业(广州)集团有限公司 | High-compaction-density rubidium-doped lithium battery positive electrode material and preparation method thereof |
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