CN105140492A - Cobalt-nickel lithium manganate composite positive electrode material with surface wrapped by lithium zirconate and preparation method - Google Patents

Cobalt-nickel lithium manganate composite positive electrode material with surface wrapped by lithium zirconate and preparation method Download PDF

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CN105140492A
CN105140492A CN201510657555.8A CN201510657555A CN105140492A CN 105140492 A CN105140492 A CN 105140492A CN 201510657555 A CN201510657555 A CN 201510657555A CN 105140492 A CN105140492 A CN 105140492A
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lithium
composite positive
nickel
lini
positive pole
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曾宪武
曾洪华
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Guangdong Tian Jing New Forms Of Energy Science And Technology Co Ltd
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Guangdong Tian Jing New Forms Of Energy Science And Technology Co Ltd
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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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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Abstract

The invention discloses a cobalt-nickel lithium manganate composite positive electrode material with the surface wrapped by lithium zirconate and a preparation method. The preparation method includes the steps of firstly, preparing LiNi0.8Co0.1Mn0.1O2 through a wet chemistry method with soluble salt of nickel, cobalt and manganese and excessive lithium salt as raw materials; secondly, mixing LiNi0.8Co0.1Mn0.1O2 with zirconium nitrate, and preparing the LiNi0.8Co0.1Mn0.1O2 composite positive electrode material with the surface wrapped by Li2ZrO3 through a rheological phase method. The LiNi0.8Co0.1Mn0.1O2 composite positive electrode material with the surface wrapped by Li2ZrO3 has the advantages of being excellent in circulation performance, good in rate capability, simple and convenient in preparation process, low in cost, and the like, and is beneficial for being applied and popularized on a large scale as the positive electrode material of lithium ion batteries.

Description

A kind of nickel cobalt lithium manganate of Surface coating lithium zirconate and preparation method
Technical field
The energy of the present invention and field of new, relate to a kind of lithium ion secondary battery anode material and preparation method, is specifically related to a kind of nickel cobalt lithium manganate and preparation method of Surface coating lithium zirconate.
Background technology
At present, lithium ion battery has been widely used in 3C industry, i.e. computer (Computer), communication (Communication) and consumer electronics (ConsumerElectronic) product, and progress into fields such as electric automobile (EV) and hybrid vehicle (HEV) electrokinetic cells that is representative.Tertiary cathode material LiNi 0.8co 0.1mn 0.1o 2because having the features such as the high and low cost of specific capacity, be considered to most possibly replace current commercial LiCoO 2one of novel anode material.
LiNi 0.8co 0.1mn 0.1o 2in nature close to LiNiO 2, can LiNiO be regarded as 2doping vario-property product, it has and is similar to LiCoO 2the same α-NaFeO 2layered rock salt structure, belongs to hexagonal crystal system, space group, is the embedding lithium composite xoide of stratiform.In crystal, Li is positioned at 3a, and O is positioned at 6c, and transition metal Co is positioned at 3b position.Ni average valence is wherein+3 valencys, has a certain proportion of Ni 2+exist, Co is+3 valencys, and Mn is+4 valencys.In charge and discharge process, the valence state of Mn keeps+4 valencys constant, does not participate in electrochemical reaction process; Co 3+oxidizing potential higher at about 4.6V, be more difficultly oxidized to Co 4+.Co and Mn shows as non-electroactive, plays the effect of rock-steady structure and lifting thermal stability in cyclic process.At Li 1-xni 0.8co 0.1mn 0.1o 2in, along with Li +deviate from (x<0.8), Ni experienced by Ni 3+/ Ni 4+, Ni 2+/ Ni 4+, Ni 2+/ Ni 3+change procedure, corresponding oxidizing potential is about 3.6 ~ 4.1V.But, along with the rising of current potential, Li 1-xni 0.8co 0.1mn 0.1o 2more lithium will be deviate from, the high electrochemical activity material making its surface easily with electrolyte generation complex reaction, reduction reversible specific capacity.Its result can cause LiNi 0.8co 0.1mn 0.1o 2the first charge-discharge efficiency of positive electrode is low, capacity attenuation is fast in cyclic process, high rate performance is poor, which greatly limits the application of this material in actual production, therefore, and LiNi 0.8co 0.1mn 0.1o 2the performance of positive electrode also has the space promoted further.
Summary of the invention
The present invention mainly solves LiNi 0.8co 0.1mn 0.1o 2be applied to high rate performance that anode material for lithium-ion batteries occurs and the poor problem of cycle performance, a kind of nickel cobalt lithium manganate and preparation method of Surface coating lithium zirconate are provided.
The invention provides a kind of nickel cobalt lithium manganate of Surface coating lithium zirconate, its technical scheme is as follows:
A nickel cobalt lithium manganate for Surface coating lithium zirconate, described composite positive pole is by LiNi 0.8co 0.1mn 0.1o 2with be attached to LiNi 0.8co 0.1mn 0.1o 2the coating layer Li on surface 2zrO 3composition, in described composite positive pole, the mol ratio of lithium, nickel, cobalt, manganese is 1.06 ~ 1.12:0.8:0.1:0.1.
Preferably, described coating layer Li 2zrO 3thickness be 0.01nm ~ 50nm.
Preferably, described coating layer Li 2zrO 3mass percent shared in composite positive pole is 0.01% ~ 5%.
In the present invention, Li 2zrO 3the reason that mass percent in the nickel cobalt lithium manganate of Surface coating lithium zirconate and thickness are restricted is, Li 2zrO 3belong to insulating material, after content and coated thickness are too large, can polarization of electrode be increased, weaken the lifting of composite material capacity, cycle performance and high rate performance.
The invention provides a kind of preparation method of nickel cobalt lithium manganate of Surface coating lithium zirconate, its technical scheme is as follows:
A preparation method for the nickel cobalt lithium manganate of Surface coating lithium zirconate, comprises the steps:
(1) taking the nickel containing certain mol proportion, cobalt, the nitrate of manganese or acetate joins in secondary deionized water, fully stirs and forms stabilizing solution or the suspending liquid A that concentration is 40g/L ~ 200g/L;
(2) take the soluble-salt of the lithium containing certain mol proportion, be dissolved in secondary deionized water, fully stir and form the stabilizing solution B that concentration is 1g/L ~ 100g/L;
(3) solution B is added drop-wise in solution or suspending liquid A by the speed of 20ml/min ~ 30ml/min, at room temperature stir 1h ~ 4h, then 8h ~ 12h is heated at this mixed solution being placed on 60 DEG C ~ 90 DEG C, Keep agitation in heating process, finally in the environment of 110 DEG C ~ 120 DEG C, heating removing moisture content obtains dry presoma;
(4) by the presoma grind into powder of previous step gained drying;
(5) presoma obtained in the previous step is calcined 4h ~ 20h at 800 DEG C ~ 950 DEG C, obtain nickel-cobalt lithium manganate cathode material;
(6) with reference to lithium content in step (2), the zirconium nitrate taking certain mass is dissolved in secondary deionized water, then the nickel-cobalt lithium manganate cathode material powder obtained in the step (5) of certain mass is added wherein, obtain stream covert, 60 DEG C ~ 90 times Keep agitation 4h ~ 8h, evaporate to dryness moisture content, calcines 2h ~ 4h at 500 DEG C ~ 800 DEG C, obtains the nickel cobalt lithium manganate of Surface coating lithium zirconate.
Preferably, described step (1) is with step (2), and the mol ratio of lithium, nickel, cobalt, manganese is 1.06 ~ 1.12:0.8:0.1:0.1.
Preferably, the soluble-salt of the lithium in described step (2) is nitrate or acetate.
Preferably, calcining heat 850 ~ 900 DEG C in described step (5), calcination time 6h ~ 14h; Mainly because of under higher calcining heat and longer calcination time, although thermal diffusion is more abundant, resulting materials two-dimensional structure stability strengthens, and layer structure is more obvious, may occur excess agglomeration, cause LiNi 0.8co 0.1mn 0.1o 2crystal structure is destroyed, and has influence on chemical property.
In the present invention, in described step (1) when adopting the acetate of nickel, cobalt, manganese, because four acetate hydrate manganese are slightly soluble in water, what therefore formed is suspending liquid A; When adopting the nitrate of nickel, cobalt, manganese, the nitrate of this three metalloid is all soluble in water, and what therefore formed is solution A.
In the present invention, the content of lithium in zirconium nitrate consumption reference step (2) of the certain mass that step (6) is mentioned, such as, due in described composite positive pole, preferably the mol ratio of lithium, nickel, cobalt, manganese is 1.06 ~ 1.12:0.8:0.1:0.1, forms kernel LiNi 0.8co 0.1mn 0.1o 2after, lithium more than needed will synthesize lithium zirconate with zirconium nitrate, and therefore according to lithium more than needed, the zirconium relative molecular weight of needs is 0.03 ~ 0.06, and particularly, the content according to lithium adjusts the addition of zirconium nitrate.
It is of the present invention that to realize principle as follows:
Due to LiNi 0.8co 0.1mn 0.1o 2all there is the phenomenon that surface reactive material dissolves when working under high potential or big current environment, therefore, select suitable coating layer material and suitable coated path, suppress LiNi 0.8co 0.1mn 0.1o 2loss when surface reactive material works under severe rugged environment, can significantly promote its chemical property, especially high rate performance.
In the present invention, first make zirconium nitrate at high temperature decompose generation zirconium dioxide, then utilize zirconium dioxide and LiNi 0.8co 0.1mn 0.1o 2the lithium reaction formation lithium zirconate (Li that surface is excessive 2zrO 3) coating layer.Li 2zrO 3have that chemical thermodynamics is stablized, the feature of electrochemicaUy inert, there is again higher lithium ion mobility speed simultaneously.Adopt Li 2zrO 3after coated, LiNi can be promoted 0.8co 0.1mn 0.1o 2surface texture stability, shielding LiNi 0.8co 0.1mn 0.1o 2the active site on surface, suppress its interfacial reaction with electrolyte, thus reach the object of its high rate performance of lifting and cycle performance.
The present invention has the following advantages:
(1), easy preparation technology can realize Li 2zrO 3effectively be coated on LiNi 0.8co 0.1mn 0.1o 2surface;
(2), the nickel cobalt lithium manganate of the Surface coating lithium zirconate of preparation has excellent cycle performance and high rate performance;
(3), raw material is cheaply easy to get;
(4), adopt wet chemistry method and Rheological Phase Method, simple process, cost are low, are suitable for large-scale production.
Accompanying drawing explanation
Fig. 1 is a kind of Surface coating Li in the embodiment of the present invention 1 2zrO 3liNi 0.8co 0.1mn 0.1o 2liNi in composite positive pole and comparative example 1 0.8co 0.1mn 0.1o 2xRD trace analysis;
Fig. 2 is a kind of Surface coating Li in the embodiment of the present invention 1 2zrO 3liNi 0.8co 0.1mn 0.1o 2eSEM (SEM) image of composite positive pole;
Fig. 3 is a kind of Surface coating Li in the embodiment of the present invention 1 2zrO 3liNi 0.8co 0.1mn 0.1o 2the cycle performance figure of composite positive pole under 1C multiplying power;
Fig. 4 is a kind of Surface coating Li in the embodiment of the present invention 1 2zrO 3liNi 0.8co 0.1mn 0.1o 2transmission electron microscope (TEM) image of composite positive pole;
Fig. 5 is a kind of Surface coating Li in the embodiment of the present invention 1 2zrO 3liNi 0.8co 0.1mn 0.1o 2liNi in composite positive pole and comparative example 1 0.8co 0.1mn 0.1o 2the high rate performance of positive electrode compares.
Embodiment
Below in conjunction with the drawings and specific embodiments, invention is described in detail.
embodiment 1
A kind of Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the preparation method of composite positive pole, its concrete steps are as follows:
(1) take 5.97g nickel acetate tetrahydrate, 0.75g tetra-acetate hydrate cobalt, 0.74g tetra-acetate hydrate manganese joins in 100ml secondary deionized water, fully stir and form the stable suspension A that concentration is 74.6g/L;
(2) taking 1.24g lithium acetate is dissolved in 100ml secondary deionized water, fully stirs and forms the stabilizing solution B that concentration is 12.4g/L;
(3) step (2) described solution B is added drop-wise in the suspending liquid A described in step (1) by the speed of 30ml/min, at room temperature stir 2h, then 8h is heated at this mixed solution being placed on 90 DEG C, Keep agitation in heating process, finally under 120 DEG C of environment, heating removing moisture obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 15min, obtain dry precursor powder;
(5) precursor powder obtained in step (4) is placed in atmosphere, at 850 DEG C, calcine 12h, obtain LiNi 0.8co 0.1mn 0.1o 2;
(6) 0.25g five water zirconium nitrate is dissolved in 30ml secondary deionized water, then adds the LiNi prepared in step (5) 0.8co 0.1mn 0.1o 2, stir and form stream in a disguised form, heat 6h, evaporate to dryness moisture content at 90 DEG C, grinding 5min, 800 DEG C of calcining 2h, prepare Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole.
The assembling of battery: the Surface coating Li taking 0.425g gained 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole, adds 0.05g acetylene black and makes conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, evenly be coated on aluminium foil after making slurry, to beat after sheet 70 DEG C, dry 12h in vacuum drying oven, obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC(volume ratio 1:1:1) be electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.6V ~ 4.3V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.The voltage range of cycle performance test is also circulate 100 times under 2.6V ~ 4.3V, 1.0C.
A kind of Surface coating Li that the present embodiment obtains 2zrO 3liNi 0.8co 0.1mn 0.1o 2the LiNi obtained in composite positive pole and comparative example 1 0.8co 0.1mn 0.1o 2the XRD collection of illustrative plates of positive electrode as shown in Figure 1, can be observed the present invention and successfully prepare above-mentioned material.
A kind of Surface coating Li that the present embodiment obtains 2zrO 3liNi 0.8co 0.1mn 0.1o 2eSEM (SEM) image of composite positive pole as shown in Figure 2, can observe LiNi 0.8co 0.1mn 0.1o 2having there is obvious attachment in the surface of particle, shows Li 2zrO 3more successfully be coated on LiNi 0.8co 0.1mn 0.1o 2the surface of particle.
The Surface coating Li that the present embodiment obtains 2zrO 3liNi 0.8co 0.1mn 0.1o 2the cycle performance figure of composite positive pole under 1.0C multiplying power as shown in Figure 3, can observe through Li 2zrO 3liNi after coated 0.8co 0.1mn 0.1o 2under 1.0C multiplying power, have good cycle performance, its first discharge specific capacity reaches 217mAh/g, and the capability retention after 100 times that circulates under 1.0C is 73.2%.
The Surface coating Li that the present embodiment obtains 2zrO 3liNi 0.8co 0.1mn 0.1o 2transmission electron microscope (TEM) image of composite positive pole as shown in Figure 4, can see LiNi in figure 0.8co 0.1mn 0.1o 2particle surface obviously has the coated material of one deck to exist, and further illustrates technique of the present invention and can realize at LiNi 0.8co 0.1mn 0.1o 2the coated Li of particle surface 2zrO 3, coating layer Li 2zrO 3thickness at about 20nm.
The Surface coating Li that the present embodiment obtains 2zrO 3liNi 0.8co 0.1mn 0.1o 2liNi in composite positive pole and comparative example 1 0.8co 0.1mn 0.1o 2the high rate performance of positive electrode more as shown in Figure 5, as can be observed from Figure, Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole has all shown and has compared LiNi under different multiplying powers 0.8co 0.1mn 0.1o 2high specific discharge capacity, illustrates Li 2zrO 3coating layer significantly can promote LiNi 0.8co 0.1mn 0.1o 2high rate performance.
embodiment 2
A kind of Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the preparation method of composite positive pole, its concrete steps are as follows:
(1) take 9.95g nickel acetate tetrahydrate, 1.25g tetra-acetate hydrate cobalt, 1.23g tetra-acetate hydrate manganese joins in 100ml secondary deionized water, fully stir and form the stable suspension A that concentration is 134.2g/L;
(2) taking 2.10g lithium acetate is dissolved in 100ml secondary deionized water, fully stirs and forms the stabilizing solution B that concentration is 21.0g/L;
(3) step (2) described solution B is added drop-wise in the suspending liquid A described in step (1) by the speed of 25ml/min, at room temperature stir 4h, then 10h is heated at this mixed solution being placed on 80 DEG C, Keep agitation in heating process, finally under 120 DEG C of environment, heating removing moisture obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 20min, obtain dry precursor powder;
(5) precursor powder obtained in step (4) is placed in atmosphere, at 800 DEG C, calcine 16h, obtain LiNi 0.8co 0.1mn 0.1o 2;
(6) 0.55g five water zirconium nitrate is dissolved in 30ml secondary deionized water, then adds the LiNi prepared in step (5) 0.8co 0.1mn 0.1o 2, stir that to form stream covert, heat 7h at 80 DEG C, evaporate to dryness moisture content, grinding 5min, 750 DEG C, calcine 3h in air atmosphere, prepare a kind of Surface coating Li of the present invention 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole.
The assembling of battery: the Surface coating Li taking 0.425g gained 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole, adds 0.05g acetylene black and makes conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, evenly be coated on aluminium foil after making slurry, to beat after sheet 70 DEG C, dry 12h in vacuum drying oven, obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.6V ~ 4.3V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.The voltage range of cycle performance test is also circulate 100 times under 2.6V ~ 4.3V, 1.0C.Electrochemical property test shows, under 0.2C, and Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the first discharge specific capacity of composite positive pole is under 210mAh/g, 3.0C, and specific discharge capacity is 158mAh/g.
embodiment 3
A kind of Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the preparation method of composite positive pole, its concrete steps are as follows:
(1) take 7.96g nickel acetate tetrahydrate, 1.00g tetra-acetate hydrate cobalt, 0.99g tetra-acetate hydrate manganese joins in 100ml secondary deionized water, fully stir and form the stable suspension A that concentration is 99.5g/L;
(2) taking 1.70g lithium nitrate is dissolved in 100ml secondary deionized water, fully stirs and forms the stabilizing solution B that concentration is 17.0g/L;
(3) step (2) described solution B is added drop-wise in the suspending liquid A described in step (1) by the speed of 30ml/min, at room temperature stir 3h, then 12h is heated at this mixed solution being placed on 70 DEG C, Keep agitation in heating process, finally under 110 DEG C of environment, heating removing moisture obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 15min, obtain dry precursor powder;
(5) precursor powder obtained in step (4) is placed in atmosphere, at 850 DEG C, calcine 12h, obtain LiNi 0.8co 0.1mn 0.1o 2;
(6) 0.55g five water zirconium nitrate is dissolved in 30ml secondary deionized water, then adds the LiNi prepared in step (5) 0.8co 0.1mn 0.1o 2, stir that to form stream covert, heat 6h at 80 DEG C, evaporate to dryness moisture content, grinding 5min, 500 DEG C, calcine 4h in air atmosphere, prepare a kind of Surface coating Li of the present invention 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole.
The assembling of battery: the Surface coating Li taking 0.425g gained 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole, adds 0.05g acetylene black and makes conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, evenly be coated on aluminium foil after making slurry, to beat after sheet 70 DEG C, dry 12h in vacuum drying oven, obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.6V ~ 4.3V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.The voltage range of cycle performance test is also circulate 100 times under 2.6V ~ 4.3V, 1.0C.Electrochemical property test shows, under 0.2C, and Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the first discharge specific capacity of composite positive pole is under 205mAh/g, 3.0C, and specific discharge capacity is 160mAh/g.
embodiment 4
A kind of Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the preparation method of composite positive pole, its concrete steps are as follows:
(1) take 3.98g nickel acetate tetrahydrate, 0.50g tetra-acetate hydrate cobalt, 0.49g tetra-acetate hydrate manganese joins in 100ml secondary deionized water, fully stir and form the stable suspension A that concentration is 49.7g/L;
(2) taking 0.83g lithium acetate is dissolved in 100ml secondary deionized water, fully stirs and forms the stabilizing solution B that concentration is 8.3g/L;
(3) step (2) described solution B is added drop-wise in the suspending liquid A described in step (1) by the speed of 30ml/min, at room temperature stir, 2h, then 12h is heated at this mixed solution being placed on 60 DEG C, Keep agitation in heating process, finally under 120 DEG C of environment, heating removing moisture obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 10min, obtain dry precursor powder;
(5) precursor powder obtained in step (4) is placed in atmosphere, at 900 DEG C, calcine 6h, obtain LiNi 0.8co 0.1mn 0.1o 2;
(6) 0.12g five water zirconium nitrate is dissolved in 30ml secondary deionized water, then adds the LiNi prepared in step (5) 0.8co 0.1mn 0.1o 2, stir that to form stream covert, heat 5h at 90 DEG C, evaporate to dryness moisture content, grinding 5min, 600 DEG C, calcine 2h in air atmosphere, prepare a kind of Surface coating Li of the present invention 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole.
The assembling of battery: the Surface coating Li taking 0.425g gained 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole, adds 0.05g acetylene black and makes conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, evenly be coated on aluminium foil after making slurry, to beat after sheet 70 DEG C, dry 12h in vacuum drying oven, obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.6V ~ 4.3V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.The voltage range of cycle performance test is also circulate 100 times under 2.6V ~ 4.3V, 1.0C.Electrochemical property test shows, under 0.2C, and Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the first discharge specific capacity of composite positive pole is under 220mAh/g, 3.0C, and specific discharge capacity is 150mAh/g.
embodiment 5
A kind of Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the preparation method of composite positive pole, its concrete steps are as follows:
(1) take 3.98g nickel acetate tetrahydrate, 0.50g tetra-acetate hydrate cobalt, 0.49g tetra-acetate hydrate manganese joins in 100ml secondary deionized water, fully stir and form the stable suspension A that concentration is 49.7g/L;
(2) taking 0.83g lithium nitrate is dissolved in 100ml secondary deionized water, fully stirs and forms the stabilizing solution B that concentration is 8.3g/L;
(3) step (2) described solution B is added drop-wise in the suspending liquid A described in step (1) by the speed of 20ml/min, at room temperature stir 2h, then 8h is heated at this mixed solution being placed on 90 DEG C, Keep agitation in heating process, finally under 120 DEG C of environment, heating removing moisture obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 15min, obtain dry precursor powder;
(5) precursor powder obtained in step (4) is placed in atmosphere, at 850 DEG C, calcine 12h, obtain LiNi 0.8co 0.1mn 0.1o 2;
(6) 0.06g five water zirconium nitrate is dissolved in 30ml secondary deionized water, then adds the LiNi prepared in step (5) 0.8co 0.1mn 0.1o 2, stir that to form stream covert, heat 6h at 90 DEG C, evaporate to dryness moisture content, grinding 5min, 800 DEG C, calcine 2h in air atmosphere, prepare a kind of Surface coating Li of the present invention 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole.
The assembling of battery: the Surface coating Li taking 0.425g gained 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole, adds 0.05g acetylene black and makes conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, evenly be coated on aluminium foil after making slurry, to beat after sheet 70 DEG C, dry 12h in vacuum drying oven, obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.6V ~ 4.3V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.The voltage range of cycle performance test is also circulate 100 times under 2.6V ~ 4.3V, 1.0C.Electrochemical property test shows, under 0.2C, and Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the first discharge specific capacity of composite positive pole is under 222mAh/g, 3.0C, and specific discharge capacity is 145mAh/g.
embodiment 6
A kind of Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the preparation method of composite positive pole, its concrete steps are as follows:
(1) take 11.94g nickel nitrate, 1.50g cobalt nitrate, 1.48g manganese nitrate be dissolved in 100ml secondary deionized water, fully stir and form the stabilizing solution A that concentration is 149.2g/L;
(2) taking 2.52g lithium nitrate is dissolved in 100ml secondary deionized water, fully stirs and forms the stabilizing solution B that concentration is 25.2g/L;
(3) step (2) described solution B is added drop-wise in the solution A described in step (1) by the speed of 25ml/min, at room temperature stir 4h, then 8h is heated at this mixed solution being placed on 90 DEG C, Keep agitation in heating process, finally under 120 DEG C of environment, heating removing moisture obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 15min, obtain dry precursor powder;
(5) precursor powder obtained in step (4) is placed in atmosphere, at 850 DEG C, calcine 12h, obtain LiNi 0.8co 0.1mn 0.1o 2;
(6) 0.08g five water zirconium nitrate is dissolved in 30ml secondary deionized water, then adds the LiNi prepared in step (5) 0.8co 0.1mn 0.1o 2, stir that to form stream covert, heat 6h at 90 DEG C, evaporate to dryness moisture content, grinding 5min, 800 DEG C, calcine 2h in air atmosphere, prepare a kind of Surface coating Li of the present invention 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole.
The assembling of battery: the Surface coating Li taking 0.425g gained 2zrO 3liNi 0.8co 0.1mn 0.1o 2composite positive pole, adds 0.05g acetylene black and makes conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, evenly be coated on aluminium foil after making slurry, to beat after sheet 70 DEG C, dry 12h in vacuum drying oven, obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.6V ~ 4.3V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.The voltage range of cycle performance test is also circulate 100 times under 2.6V ~ 4.3V, 1.0C.Electrochemical property test shows, under 0.2C, and Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the first discharge specific capacity of composite positive pole is under 217mAh/g, 3.0C, and specific discharge capacity is 145mAh/g.
comparative example 1
A kind of LiNi 0.8co 0.1mn 0.1o 2the preparation method of positive electrode, its concrete steps are as follows:
(1) take 5.97g nickel acetate tetrahydrate, 0.75g tetra-acetate hydrate cobalt, 0.74g tetra-acetate hydrate manganese joins in 100ml secondary deionized water, fully stir and form the stable suspension A that concentration is 74.6g/L;
(2) taking 1.24g lithium acetate is dissolved in 100ml secondary deionized water, fully stirs and forms the stabilizing solution B that concentration is 12.4g/L;
(3) step (2) described B solution is added drop-wise in the suspending liquid A described in step (1) by the speed of 30ml/min, at room temperature stir 4h, then 8h is heated at this mixed solution being placed on 90 DEG C, Keep agitation in heating process, finally under 120 DEG C of environment, heating removing moisture obtains dry presoma;
(4) presoma of gained in step (3) is placed in dry environment grinds 15min, obtain dry precursor powder;
(5) precursor powder obtained in step (4) is placed in atmosphere, at 850 DEG C, calcine 12h, obtain LiNi 0.8co 0.1mn 0.1o 2;
The assembling of battery: the LiNi taking 0.425g gained 0.8co 0.1mn 0.1o 2positive electrode, adds 0.05g acetylene black and makes conductive agent and 0.025gLA-132 makes binding agent, even ground and mixed in agate mortar, evenly be coated on aluminium foil after making slurry, to beat after sheet 70 DEG C, dry 12h in vacuum drying oven, obtained electrode slice, puts into glove box.With this electrode slice for work electrode, lithium metal is to electrode, and Celgard2400 is barrier film, 1mol/LLiPF 6/ EC:DEC:DMC (volume ratio 1:1:1) is electrolyte, assembling composition CR2032 button cell.
At room temperature carry out constant current charge-discharge test, the test voltage scope of high rate performance is 2.6V ~ 4.3V, and charge-discharge magnification is each 10 times of 0.2C, 0.5C, 1.0C, 2.0C, 3.0C, finally circulates 30 times under 0.2C.The voltage range of cycle performance test is also circulate 100 times under 2.6V ~ 4.3V, 1.0C.
LiNi in comparative example 1 0.8co 0.1mn 0.1o 2surface coating Li in positive electrode and embodiment 1 2zrO 3liNi 0.8co 0.1mn 0.1o 2the high rate performance of composite positive pole as Fig. 5, LiNi in comparative example 1 0.8co 0.1mn 0.1o 2the first discharge specific capacity of positive electrode under 0.2C is 205mAh/g, lower than Surface coating Li in embodiment 1 2zrO 3liNi 0.8co 0.1mn 0.1o 2the capacity of composite positive pole under this multiplying power, in addition, along with the raising of multiplying power, Surface coating Li 2zrO 3liNi 0.8co 0.1mn 0.1o 2the high rate performance advantage of composite positive pole more significantly embodies.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.

Claims (7)

1. a nickel cobalt lithium manganate for Surface coating lithium zirconate, is characterized in that, described composite material is by LiNi 0.8co 0.1mn 0.1o 2be attached to LiNi 0.8co 0.1mn 0.1o 2the coating layer Li on surface 2zrO 3composition, in described composite positive pole, the mol ratio of lithium, nickel, cobalt, manganese is 1.06 ~ 1.12:0.8:0.1:0.1.
2. composite positive pole according to claim 1, is characterized in that, coating layer Li 2zrO 3thickness be 0.01nm ~ 50nm.
3. composite positive pole according to claim 1, is characterized in that, coating layer Li 2zrO 3mass percent shared in described composite positive pole is 0.01% ~ 5%.
4. a preparation method for the nickel cobalt lithium manganate of Surface coating lithium zirconate, is characterized in that, comprises the steps:
(1) taking the nickel containing certain mol proportion, cobalt, the nitrate of manganese or acetate joins in secondary deionized water, fully stirs and forms stabilizing solution or the suspending liquid A that concentration is 40g/L ~ 200g/L;
(2) take the soluble-salt of the lithium containing certain mol proportion, be dissolved in secondary deionized water, fully stir and form the stabilizing solution B that concentration is 1g/L ~ 100g/L;
(3) solution B is added drop-wise in solution or suspending liquid A by the speed of 20ml/min ~ 30ml/min, at room temperature stir 1h ~ 4h, then 8h ~ 12h is heated at this mixed solution being placed on 60 DEG C ~ 90 DEG C, Keep agitation in heating process, finally in the environment of 110 DEG C ~ 120 DEG C, heating removing moisture content obtains dry presoma;
(4) by the presoma grind into powder of previous step gained drying;
(5) precursor powder obtained in the previous step is calcined 4h ~ 20h at 800 DEG C ~ 950 DEG C, obtain nickel-cobalt lithium manganate cathode material;
(6) with reference to lithium content in step (2), the zirconium nitrate taking certain mass is dissolved in secondary deionized water, then adds wherein by the nickel-cobalt lithium manganate cathode material powder obtained in the step (5) of certain mass, obtains stream covert, Keep agitation 4 ~ 8h at 60 DEG C ~ 90 DEG C, evaporate to dryness moisture content; Calcine 2h ~ 4h at 500 DEG C ~ 800 DEG C, obtain the nickel cobalt lithium manganate of Surface coating lithium zirconate.
5. the preparation method of composite positive pole according to claim 4, is characterized in that, described step (1) is with step (2), and the mol ratio of lithium, nickel, cobalt, manganese is 1.06 ~ 1.12:0.8:0.1:0.1.
6. the preparation method of composite positive pole according to claim 4, is characterized in that, in described step (2), the soluble-salt of lithium is nitrate or acetate.
7. the preparation method of composite positive pole according to claim 4, is characterized in that, calcining heat 850 DEG C ~ 900 DEG C in described step (5), calcination time is 6h ~ 14h.
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