CN105680018A - Ternary positive electrode material and preparation method therefor and lithium ion battery - Google Patents
Ternary positive electrode material and preparation method therefor and lithium ion battery Download PDFInfo
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- CN105680018A CN105680018A CN201610130536.4A CN201610130536A CN105680018A CN 105680018 A CN105680018 A CN 105680018A CN 201610130536 A CN201610130536 A CN 201610130536A CN 105680018 A CN105680018 A CN 105680018A
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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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- 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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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of a battery, and specifically discloses a ternary positive electrode material and a preparation method therefor and a lithium ion battery. The preparation method comprises the steps of (1) mixing tetraethyl orthosilicate, an organic solvent, water and an Ni-Co-Mn ternary material precursor; then removing the organic solvent and water from the mixture obtained by mixing so as to obtain a solid product; mixing the solid product obtained in the step (1) with a lithium salt, and calcining the mixture under an oxygen atmosphere. The invention also provides the ternary positive electrode material; the ternary positive electrode material contains Li2SiO3 and LiNiaCobMncO2, wherein a, b and c are all greater than 0 and less than 1; and a+b+c is equal to 1. The ternary positive electrode material provided by the invention has relatively high rate capability and cycling stability.
Description
Technical field
The present invention relates to field of batteries, specifically, it relates to a kind of tertiary cathode material and its preparation method and a kind of lithium ion battery.
Background technology
Along with the scarcity of environmental degradation and fossil type Nonrenewable resources, people are more and more urgent to the demand of new forms of energy instantly. As the lithium ion battery of a kind of green energy resource, since the beginning of the nineties in last century successfully develops, just low with its specific energy height, operating voltage height, application of temperature wide ranges, self-discharge rate, have extended cycle life, the unique advantage such as pollution-free and receive much attention, widespread use in the small-sized portable electronic products such as mobile phone, digital camera, notebook computer, and become one of topmost candidate's electrical source of power of electromobile gradually. But, along with high-technicalization, the miniaturization of the development of electronic digital product renewal acceleration, new forms of energy industry and military equipment, the energy density of lithium ion battery, safe reliability and cycle life being had higher requirement, the high specific energyization therefore how promoting present stage business-like positive electrode material is the emphasis of research always.
Current business-like anode material for lithium-ion batteries is mainly laminated ternary positive material LiNiaCobMncO2(0 < a, b, c < 1, a+b+c=1), in order to obtain high energy density, one is the proportion increasing Ni in material, under common stopping potential (not higher than 4.3V), material is along with the increase of Ni content, and specific storage increases, but its cyclical stability, thermal safety etc. present downtrending; Two is the discharge and recharge stopping potential (being greater than 4.3V) promoting material, and along with the lifting of voltage, specific storage improves, but cyclical stability, thermal safety etc. are also on a declining curve. Above two kinds of situations are all owing to material material surface in process of charging is easy and electrolytic solution generation side reaction, cause the charge transfer impedance Rct of material to increase, the uncontrollable initiation thermal runaway of simultaneous reactions, and then affect the chemical property of material.
Current surface coating method has been widely used in promoting modification of lithium ion battery anode material preparation, obviously improves the cyclical stability of material, thermal safety etc. CN103094553A discloses a kind of AlF3Coated layered cathode material Li1+xM1-xO2(M can be one or more in Ni, Co, Mn, Al, 0≤x≤1/3), AlF3For the non-fast-ionic conductor of one, although improving the cyclical stability of material, but the lifting for high rate performance is not significantly contributed.
Summary of the invention
The defects such as the high rate performance that it is an object of the invention to overcome existing lithium ion anode material is poor, cyclical stability difference, it is provided that a kind of high rate performance and the excellent tertiary cathode material of stable circulation performance and its preparation method and lithium ion battery.
In order to realize above-mentioned purpose, the present invention provides a kind of tertiary cathode material, and wherein, this tertiary cathode material contains Li2SiO3And LiNiaCobMncO2, wherein, a, b and c are all greater than 0 and be less than 1, and a+b+c=1.
The present invention is by conventional LiNiaCobMncO2Material adds fast-ionic conductor Li2SiO3, it is to increase the cyclical stability of material and high rate performance, in a preferred embodiment of the invention, by fast-ionic conductor Li2SiO3It is coated on LiNiaCobMncO2Positive electrode material surface, further increases cyclical stability and the high rate performance of material.
The present invention also provides the preparation method of a kind of tertiary cathode material, and wherein, the method comprises:
(1) by tetraethyl orthosilicate, organic solvent, water and the mixing of Ni-Co-Mn ternary material precursor, then de-except the organic solvent in the mixture being mixed to get and water are to obtain solid product;
(2) solid product that step (1) obtains is mixed with lithium salt, then calcine under an oxygen-containing atmosphere.
Present invention also offers the tertiary cathode material obtained by aforesaid method.
Present invention also offers a kind of lithium ion battery, wherein, the positive electrode material of described lithium ion battery comprises above-mentioned tertiary cathode material.
Method provided by the invention makes fast-ionic conductor Li2SiO3It is coated on LiNiaCobMncO2Positive electrode material surface, calcining facilitates the complete and Stability Analysis of Structures of brilliant type, and what make that lithium ion diffusion admittance formed is more complete, and channel architecture firmly, thus is conducive to lithium ion to spread, it is to increase high rate performance. Simultaneously stable structure can reduce the volumetric shrinkage in working cycle and crystal subsides, and therefore has better cyclical stability.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention with embodiment one below, but is not construed as limiting the invention. In the accompanying drawings:
Fig. 1 is that embodiment 1 obtains the XRD figure (see curve 1) of tertiary cathode material S-1 and comparative example 1 obtains the XRD figure (see curve 2) of tertiary cathode material D-1.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail. Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The present invention provides a kind of tertiary cathode material, and wherein, this tertiary cathode material contains Li2SiO3And LiNiaCobMncO2, wherein, a, b and c are all greater than 0 and be less than 1, and a+b+c=1.
In the present invention, the span of a, b and c is wider, as long as meeting a, b and c be all greater than 0 and be less than 1, and a+b+c=1, it may be preferred that a is more than or equal to 0.3 and be less than 1; B is greater than 0 and be less than or equal to 0.4; C is greater than 0 and be less than 0.4.
A preferred embodiment of the invention, in described tertiary cathode material, described Li2SiO3With described LiNiaCobMncO2Mol ratio be (0.5-10): 100, further preferred described Li2SiO3With described LiNiaCobMncO2Mol ratio be (3-10): 100. Adopt this preferred content can improve cyclical stability and the high rate performance of tertiary cathode material further.
A preferred embodiment of the invention, described Li2SiO3It is coated on LiNiaCobMncO2Outside surface, this kind of preferred implementation can improve cyclical stability and the high rate performance of material further.
As long as tertiary cathode material provided by the invention has the object that preceding feature can realize the present invention, to its preparation method without particular requirement, every method that can prepare the tertiary cathode material to have preceding feature and character all can be used for the present invention, for the present invention, preferred tertiary cathode material is prepared as follows, and the method comprises:
(1) by tetraethyl orthosilicate, organic solvent, water and the mixing of Ni-Co-Mn ternary material precursor, then de-except the organic solvent in the mixture being mixed to get and water are to obtain solid product;
(2) solid product that step (1) obtains is mixed with lithium salt, then calcine under an oxygen-containing atmosphere.
The present invention adopts and first makes tetraethyl orthosilicate and Ni-Co-Mn ternary material precursor mix, then with lithium salt effect, and the method calcined under an oxygen-containing atmosphere so that fast-ionic conductor Li2SiO3It is coated on LiNiaCobMncO2Positive electrode material surface, calcines the complete and Stability Analysis of Structures facilitating the brilliant type of obtained tertiary cathode material especially under an oxygen-containing atmosphere, and what make that lithium ion diffusion admittance formed is more complete, and channel architecture firmly, thus is conducive to lithium ion to spread, it is to increase high rate performance. Simultaneously stable structure can reduce the volumetric shrinkage in working cycle and crystal subsides, and therefore has better cyclical stability.
In the present invention, the mode of described tetraethyl orthosilicate, organic solvent, water and the mixing of Ni-Co-Mn ternary material precursor is had no particular limits, in order to make it mix, preferably first tetraethyl orthosilicate is dripped in organic solvent and water, then add Ni-Co-Mn ternary material precursor.
In the present invention, it is preferable that step (1) takes off except the organic solvent in the mixture being mixed to get and water comprise to obtain the enforcement mode of solid product:
Stir at normal temperatures, then stir at 40-80 DEG C, be dried after solution steaming is dry.
The time stirred under described normal temperature and stir at 40-80 DEG C is had no particular limits by the present invention, as long as being steamed by solution dry.
A preferred embodiment of the invention, in order to completely de-except organic solvent and water are to obtain solid product, it is preferable that being dried after solution steaming is dry, the temperature of further preferred described drying is 50-100 DEG C, is further preferably 75 DEG C.
The time of described drying is had no particular limits, it is preferable to 10-30h, further it is preferably 24h.
A preferred embodiment of the invention, the consumption of described tetraethyl orthosilicate, Ni-Co-Mn ternary material precursor and lithium salt makes Li in the tertiary cathode material prepared2SiO3With LiNiaCobMncO2Mol ratio be (0.5-10): 100, it is preferable to (3-10): 100, wherein a, b and c are all greater than 0 and be less than 1, and a+b+c=1. The consumption of this preferred tetraethyl orthosilicate, Ni-Co-Mn ternary material precursor and lithium salt is adopted more to be conducive to Li2SiO3At LiNiaCobMncO2Surperficial is coated, is conducive to improving further cyclical stability and the high rate performance of tertiary cathode material.
According to the present invention, it may be preferred that the volume ratio of described organic solvent and water is 1:(0.01-1).
In the present invention, the consumption of preferred lithium salt is more than the amount according to lithium salt needed for stoichiometric ratio technology, those skilled in the art can practical situation select, it is preferable that the consumption of described lithium salt is (1-1.1) with the mol ratio of the amount stoichiometrically calculating required lithium salt: 1. Owing to lithium salt exists Evaporation Phenomenon in reaction process, this preferred consumption can ensure Li in obtained tertiary cathode material2SiO3Content.
According to the present invention, it may be preferred that the mol ratio of described tetraethyl orthosilicate and Ni-Co-Mn ternary material precursor is (0.5-10): 100, more preferably (2-9): 100.
In the present invention, optional a wider range of described organic solvent, as long as being the organic solvent of easily volatilization, it is preferable that described organic solvent be selected from ethanol, acetone and ether one or more, more preferably ethanol.
In the present invention, described Ni-Co-Mn ternary material precursor is the Ni-Co-Mn ternary material precursor that this area is commonly used, preferably, described Ni-Co-Mn ternary material precursor be selected from the oxyhydroxide of Ni-Co-Mn, carbonate and oxalate one or more.
In the present invention, described Ni-Co-Mn ternary material precursor can be commercially available, can also by preparing, the preparation method of described Ni-Co-Mn ternary material precursor is had no particular limits by the present invention, can being the conventional any method preparing Ni-Co-Mn ternary material precursor in this area, those skilled in the art can carry out appropriate selection according to practical situation.
In the present invention, to described lithium salt, there is no particular limitation, can be the conventional various lithium salt in this area, it is preferable that described lithium salt be selected from Quilonum Retard, lithium nitrate, lithium hydroxide, Lithium Acetate, lithium oxalate and lithium chloride one or more, more preferably Quilonum Retard and/or lithium nitrate.
The mode that the present invention mixes with lithium salt for step (2) described solid matter has no particular limits, as long as can mix, it is preferable that the enforcement mode that solid matter mixes with lithium salt is for grind solid matter and lithium salt.
In the present invention, it is preferable that step (2) described calcining is sectional type calcining, and the condition of further preferred described sectional type calcining comprises: first processes 2-6h at 400-550 DEG C, then processes 8-24h at 700-950 DEG C.
In the present invention, it is preferable that step (2) described calcining rises to 400-550 DEG C from normal temperature, rises to the temperature rise rate of 700-950 DEG C by 400-550 DEG C is 1-10 DEG C/min, more preferably 3-6 DEG C/min.
Further preferred steps (2) described calcining carries out in tube furnace.
In the present invention, it is preferable that step (2) described oxygen-containing atmosphere is provided by least one in oxygen and air.
Adopt above-mentioned preferred calcining manners more to be conducive to promoting the complete and Stability Analysis of Structures of the brilliant type of tertiary cathode material, so make that lithium ion diffusion admittance formed more complete, channel architecture firmly, thus is conducive to lithium ion to spread, it is to increase high rate performance.
Present invention also offers the tertiary cathode material obtained by the preparation method by above-mentioned tertiary cathode material.
Above-mentioned tertiary cathode material provided by the present invention contains Li2SiO3And LiNiaCobMncO2, wherein, a, b and c are all greater than 0 and be less than 1, and a+b+c=1, it is preferable that Li2SiO3It is coated on LiNiaCobMncO2Outside surface; Preferred Li2SiO3With described LiNiaCobMncO2Mol ratio be (0.5-10): 100. This tertiary cathode material has the laminate structure of standard, and under preferable case, fast-ionic conductor Li2SiO3Evenly it is coated on LiNiaCobMncO2Outside surface, more effectively improve cyclical stability and the high rate performance of material.
Present invention also offers a kind of lithium ion battery, wherein, the positive electrode material of described lithium ion battery comprises above-mentioned tertiary cathode material.
Hereinafter will be described the present invention by embodiment.
Embodiment 1
The present embodiment is for illustration of the tertiary cathode material of the present invention and its preparation method.
(1) 0.1g tetraethyl orthosilicate is added drop-wise in 40ml aqueous ethanolic solution (volume ratio of ethanol and water is 100:1), then adds 1.5gNi0.6Co0.2Mn0.2(OH)2(coprecipitation method preparation), is warming up to 50 DEG C and stirs 350min under normal temperature after stirring, then dry 24h at 75 DEG C;
(2) solid matter step (1) obtained and 0.65g Quilonum Retard grind after evenly, it is placed in the tube furnace calcining of oxygen atmosphere, heat up (temperature rise rate 5 DEG C/min) to 500 DEG C, after constant temperature process 3h, heat up (temperature rise rate 5 DEG C/min) to 850 DEG C, constant temperature process 12h. Tertiary cathode material S-1 is obtained after being down to room temperature. Calculate according to charging capacity, Li in S-12SiO3Content be 2.9 moles of %; And Li2SiO3It is coated on LiNi0.6Co0.2Mn0.2O2Outside surface.
The XRD figure of tertiary cathode material S-1 is as shown in Fig. 1 curve 1.
Obtained tertiary cathode material S-1 is applied in lithium ion battery, carries out cycle performance and high rate performance test:
Using tertiary cathode material as working electrode, metallic lithium is to electrode, the LiF of 1mol/L6/ EC-DMC-EMC (volume ratio 1: 1:1) is electrolytic solution, is assembled into simulated battery, simulated battery is carried out charge-discharge test in argon gas atmosphere glove box, and voltage range is 2.8-4.6V (vs.Li+/Li)。
Test result shows, and tertiary cathode material S-1 first discharge specific capacity under 0.2C multiplying power is 196.9mAh g-1, circulation 100 circle capability retention is 85.5%; Charging under 0.2C multiplying power, after 50 circles that circulate under 10C discharge-rate, specific discharge capacity is 126.2mAh g-1, capability retention is 80%.
Comparative example 1
(1) by 1.5gNi0.6Co0.2Mn0.2(OH)2After the grinding evenly of 0.65g Quilonum Retard, be placed in the tube furnace calcining of oxygen atmosphere, heat up (temperature rise rate 5 DEG C/min) to 500 DEG C, after constant temperature process 3h, heat up (temperature rise rate 5 DEG C/min) to 850 DEG C, constant temperature process 12h. Tertiary cathode material D-1 is obtained after being down to room temperature.
The XRD figure of tertiary cathode material D-1 as shown in Fig. 1 curve 2, as can be seen from Figure 1, although tertiary cathode material S-1 provided by the invention has Li2SiO3It is coated on LiNi0.6Co0.2Mn0.2O2Outside surface, but compared with D-1 prepared by comparative example 1, there is no assorted peak, illustrate that S-1 is without assorted phase, surface coated Li2SiO3Not being doped in this phase, diffraction peak sharply illustrates S-1 good crystallinity.
Obtained tertiary cathode material D-1 is applied in lithium ion battery, carries out cycle performance as described in Example 1 and high rate performance test:
Test result shows, and tertiary cathode material D-1 first discharge specific capacity under 0.2C multiplying power is 199mAh g-1, circulation 100 circle capability retention is 75.5%; Charging under 0.2C multiplying power, after 50 circles that circulate under 10C discharge-rate, specific discharge capacity is 65mAh g-1, capability retention is 58.3%.
Comparative example 2
According to the method described in CN103094553A, take the Al (NO of 0.1786g respectively3)3·9H2The NH of O and 0.0529g4F, adds 10ml deionized water respectively, stirs 1h and dissolves completely. Utilize mass concentration be 5% NaOH solution regulate aluminum nitrate solution pH be 8, then take 2.5gLiNi0.6Co0.2Mn0.2O2, join in aluminum nitrate solution, stir 0.5h and obtain uniform mixture, then ammonium fluoride solution is slowly added drop-wise in said mixture, continue to stir 10h. Collect product, then take out filter, washing three times, sample is put into vacuum drying oven 80 DEG C and spends the night. Finally by material 400 degree of sintering 10h in high-purity argon gas, obtain AlF3The LiNi of surface coating modification0.6Co0.2Mn0.2O2。
The AlF that will obtain3The LiNi of surface coating modification0.6Co0.2Mn0.2O2It is applied in lithium ion battery, carries out cycle performance as described in Example 1 and high rate performance test.
Test result shows, AlF3The LiNi of surface coating modification0.6Co0.2Mn0.2O2Under 0.2C multiplying power, first discharge specific capacity is 196mAh g-1, circulation 100 circle capability retention is 81.6%;Charging under 0.2C multiplying power, after 50 circles that circulate under 10C discharge-rate, specific discharge capacity is 80mAh g-1, capability retention is 65.3%.
Embodiment 2
The present embodiment is for illustration of the tertiary cathode material of the present invention and its preparation method.
(1) 0.3g tetraethyl orthosilicate is added drop-wise in 40ml aqueous ethanolic solution (volume ratio of ethanol and water is 1:0.5), then adds 1.5gNi0.4Co0.2Mn0.4(OH)2(coprecipitation method preparation), is warming up to 60 DEG C and stirs 350min under normal temperature after stirring, then dry 24h at 75 DEG C; ;
(2) solid matter step (1) obtained and 1.4g lithium nitrate grind after evenly, it is placed in the tube furnace calcining of air atmosphere, heat up (temperature rise rate 3 DEG C/min) to 400 DEG C, after constant temperature process 6h, heat up (temperature rise rate 5 DEG C/min) to 950 DEG C, constant temperature process 8h. Tertiary cathode material S-2 is obtained after being down to room temperature. Calculate according to charging capacity, Li in S-22SiO3Content be 10 moles of %, and Li2SiO3It is coated on LiNi0.4Co0.2Mn0.4O2Outside surface.
The XRD figure of tertiary cathode material S-2 is similar to the XRD figure of tertiary cathode material S-1 in embodiment 1.
Obtained tertiary cathode material S-2 is applied in lithium ion battery, carries out cycle performance as described in Example 1 and high rate performance test.
Test result shows, and tertiary cathode material S-2 first discharge specific capacity under 0.2C multiplying power is 190.9mAh g-1, circulation 100 circle capability retention is 87.3%; Charging under 0.2C multiplying power, after 50 circles that circulate under 10C discharge-rate, specific discharge capacity is 79.36mAh g-1, capability retention is 73%.
Embodiment 3
The present embodiment is for illustration of the tertiary cathode material of the present invention and its preparation method.
(1) drip 0.08g tetraethyl orthosilicate to add and it is added drop-wise in 40ml aqueous ethanolic solution (volume ratio of ethanol and water is 1:1), then add 1.5gNi1/3Co1/3Mn1/3CO3(coprecipitation method preparation), is warming up to 70 DEG C and stirs 300min under normal temperature after stirring, then dry 24h at 75 DEG C;
(2) solid matter step (1) obtained and 0.52g Quilonum Retard grind after evenly, it is placed in the tube furnace calcining of oxygen atmosphere, heat up (temperature rise rate 6 DEG C/min) to 550 DEG C, after constant temperature process 2h, heat up (temperature rise rate 4 DEG C/min) to 700 DEG C, constant temperature process 24h. Tertiary cathode material S-3 is obtained after being down to room temperature. Calculate according to charging capacity, Li in S-32SiO3Content be 3.2 moles of %, and Li2SiO3It is coated on LiNi1/3Co1/3Mn1/3O2Outside surface.
The XRD figure of tertiary cathode material S-3 is similar to the XRD figure of tertiary cathode material S-1 in embodiment 1.
Obtained tertiary cathode material S-3 is applied in lithium ion battery, carries out cycle performance as described in Example 1 and high rate performance test.
Test result shows, and tertiary cathode material S-3 first discharge specific capacity under 0.2C multiplying power is 186.2mAh g-1, circulation 100 circle capability retention is 87.3%; Charging under 0.2C multiplying power, after 50 circles that circulate under 10C discharge-rate, specific discharge capacity is 95.6mAh g-1, capability retention is 85.3%.
Embodiment 4
The present embodiment is for illustration of the tertiary cathode material of the present invention and its preparation method.
Tertiary cathode material is prepared according to the method for embodiment 1, the difference is that, the amount of the tetraethyl orthosilicate added in step (1) is 0.05g, obtained tertiary cathode material S-4. Li in S-42SiO3Content be 1.5 moles of %, and Li2SiO3It is coated on LiNi0.6Co0.2Mn0.2O2Outside surface.
The XRD figure of tertiary cathode material S-4 is similar to the XRD figure of tertiary cathode material S-1 in embodiment 1.
Obtained tertiary cathode material S-4 is applied in lithium ion battery, carries out cycle performance as described in Example 1 and high rate performance test.
Test result shows, and tertiary cathode material S-4 first discharge specific capacity under 0.2C multiplying power is 199.5mAh g-1, circulation 100 circle capability retention is 81.2%; Charging under 0.2C multiplying power, after 50 circles that circulate under 10C discharge-rate, specific discharge capacity is 70.9mAh g-1, capability retention is 74%.
Embodiment 5
The present embodiment is for illustration of the tertiary cathode material of the present invention and its preparation method.
Tertiary cathode material is prepared according to the method for embodiment 1, the difference is that, the condition of step (2) described calcining is: heat up (temperature rise rate 5 DEG C/min), to 800 DEG C, constant temperature process 15h, obtains tertiary cathode material S-5.
The XRD figure of tertiary cathode material S-5 is similar to the XRD figure of tertiary cathode material S-1 in embodiment 1.
Obtained tertiary cathode material S-5 is applied in lithium ion battery, carries out cycle performance as described in Example 1 and high rate performance test.
Test result shows, and tertiary cathode material S-5 first discharge specific capacity under 0.2C multiplying power is 193.4mAh g-1, circulation 100 circle capability retention is 80.4%; Charging under 0.2C multiplying power, after 50 circles that circulate under 10C discharge-rate, specific discharge capacity is 84.6mAh g-1, capability retention is 72%.
From the contrast of embodiment 1-5 and comparative example 1-2 it may be seen that tertiary cathode material provided by the invention has good high rate performance and cycle performance.
Below the preferred embodiment of the present invention is described in detail; but, the detail that the present invention is not limited in above-mentioned enforcement mode, within the scope of the technical conceive of the present invention; the technical scheme of the present invention can being carried out multiple simple variant, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technology feature described in above-mentioned embodiment, when not contradiction, it is possible to combined by any suitable mode, in order to avoid unnecessary repetition, various possible array mode is illustrated by the present invention no longer separately.
In addition, can also carrying out arbitrary combination between the various different enforcement mode of the present invention, as long as it does not run counter to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a tertiary cathode material, it is characterised in that, this tertiary cathode material contains Li2SiO3And LiNiaCobMncO2, wherein, a, b and c are all greater than 0 and be less than 1, and a+b+c=1.
2. tertiary cathode material according to claim 1, wherein, described Li2SiO3With described LiNiaCobMncO2Mol ratio be (0.5-10): 100, it is preferable to (3-10): 100.
3. tertiary cathode material according to claim 1 and 2, wherein, described Li2SiO3It is coated on LiNiaCobMncO2Outside surface.
4. the preparation method of a tertiary cathode material, it is characterised in that, the method comprises:
(1) by tetraethyl orthosilicate, organic solvent, water and the mixing of Ni-Co-Mn ternary material precursor, then de-except the organic solvent in the mixture being mixed to get and water are to obtain solid product;
(2) solid product that step (1) obtains is mixed with lithium salt, then calcine under an oxygen-containing atmosphere.
5. preparation method according to claim 4, wherein,
The consumption of described tetraethyl orthosilicate, Ni-Co-Mn ternary material precursor and lithium salt makes Li in the tertiary cathode material prepared2SiO3With LiNiaCobMncO2Mol ratio be (0.5-10): 100, it is preferable to (3-10): 100, wherein a, b and c are all greater than 0 and be less than 1, and a+b+c=1,
Preferably, the volume ratio of described organic solvent and water is 1:(0.01-1);
Preferably, the mol ratio of described tetraethyl orthosilicate and Ni-Co-Mn ternary material precursor is (0.5-10): 100.
6. preparation method according to claim 4 or 5, wherein, described organic solvent be selected from ethanol, acetone and ether one or more, it is preferable to ethanol;
Preferably, described Ni-Co-Mn ternary material precursor be selected from the oxyhydroxide of Ni-Co-Mn, carbonate and oxalate one or more;
Preferably, described lithium salt be selected from Quilonum Retard, lithium nitrate, lithium hydroxide, Lithium Acetate, lithium oxalate and lithium chloride one or more.
7. preparation method according to claim 4 or 5, wherein, de-in step (1) comprises to obtain the enforcement mode of solid product except the organic solvent in the mixture being mixed to get and water:
Stirring at normal temperatures, then stir at 40-80 DEG C, thing to be mixed steams after doing and is dried;
Preferably, the temperature of described drying is 50-100 DEG C.
8. preparation method according to claim 4 or 5, wherein, step (2) described calcining is sectional type calcining, and the condition of described sectional type calcining comprises: first processes 2-6h at 400-550 DEG C, then processes 8-24h at 700-950 DEG C.
9. preparation method according to claim 4 or 5, wherein, step (2) described oxygen-containing atmosphere is provided by least one in oxygen and air.
10. by the tertiary cathode material that method described in any one in claim 4-9 is obtained.
11. 1 kinds of lithium ion batteries, it is characterised in that, the positive electrode material of described lithium ion battery comprises in claim 1-3 and 10 tertiary cathode material described in any one.
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