CN102800840B - Cathode material of lithium ion battery, and preparation method thereof and lithium ion battery - Google Patents
Cathode material of lithium ion battery, and preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention provides a cathode material of a lithium ion battery. The cathode material is composed by the atomic ratio shown in formula (I): Lia(MxMn2-x)(O4-yZy), wherein a is greater than or equal to 0.8 and less than or equal to 1.2; x is greater than or equal to 0 and less than or equal to 1; y is greater than or equal to 0 and less than or equal to 1; M is one or more selected from Li, Na, K, Ca, Mg, Al, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, La, Ce, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Pb and Si; and Z is one or more selected from OH, halogens, N, P, S and O. Primary particles of the cathode material have sphere-like morphologies, wherein (111) face is connected with adjacent equivalent crystal face through a curved surface having no clear edges. The invention also provides a preparation method for the cathode material of the lithium ion battery and the lithium ion battery. The cathode material provided by the invention has good high-temperature cycling performance and good filling property.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of anode material for lithium-ion batteries, its preparation method and lithium ion battery.
Background technology
Lithium ion battery is a kind of rechargeable battery, and main dependence lithium ion between a positive electrode and a negative electrode movement realizes discharge and recharge.Lithium ion battery has that fail safe is good, voltage and the advantage such as specific energy is high, the discharge and recharge life-span is long, is thus widely used in the portable electronics such as mobile phone, notebook computer and video camera.
Positive electrode is the core of lithium ion battery, prior art discloses multiple anode material for lithium-ion batteries, as lithium cobalt oxygen, LiFePO4, lithium manganese oxygen etc., wherein, lithium cobalt oxygen has the advantage such as high power capacity, high voltage, easily preparation, but cobalt is expensive and can to environmental danger; LiFePO4 has that fail safe is high, the advantage such as have extended cycle life, but its electrode machining performance is bad, consistency is poor; Lithium manganese oxygen is a kind of material with three-dimensional lithium ion tunnel, has that price is low, current potential is high, environmental friendliness, security performance advantages of higher, and lithium manganese oxygen material is adapted at the application of the large energy accumulation battery aspects such as electric motor car, thus becomes one of study hotspot.But the lithium ion battery being positive pole with lithium manganese oxygen has the shortcoming of high temperature cyclic performance difference, limits it and applies further.
Existing study general thinks that the specific area of lithium manganese oxygen is one of key factor affecting high-temperature lithium ion battery cycle performance, low specific area can reduce the contact of lithium manganese oxygen material and electrolyte, thus reduce the dissolving of manganese, improve the high temperature cyclic performance of lithium ion battery.General oxide or the fluoride of adopting carries out to lithium manganese oxygen material the lithium manganese oxygen that method that is coated or other element high temperature sinterings that adulterate obtains low specific surface area at present.The Chinese patent literature being CN1787254 as publication number discloses a kind of anode material for lithium-ion batteries, first soluble metallic salt is dissolved in solvent, then add spinel lithium manganate or derivatives thereof and form suspension-turbid liquid, by roasting after described suspension-turbid liquid spray drying granulation, obtain the spinel lithium manganate that Surface coating has metal oxide, although the coated high-temperature behavior improving lithium manganese oxygen material to a certain extent, but the coated production stage adding spinel lithium manganate, and be difficult to the consistency ensureing product.
Publication number is that the Chinese patent literature of CN1455466 discloses a kind of constitutionally stable spinel lithium manganate, obtained by electrolytic manganese dioxide, lithium carbonate, cobalt oxide and the multi-element doping body at high temperature roasting that is made up of nickel, chromium, iron, manganese, selenium and fluorine, the method increase the cycle performance of LiMn2O4, but its high temperature cyclic performance is still lower.Publication number is the LiMn2O4 that the Chinese patent literature of CN101587950 discloses a kind of micron order regular octahedron monocrystalline composition, obtains by the composite oxides of manganese and modified metal M to be mixed rear roasting with lithium salts ball milling.The lithium manganese oxygen material specific surface area that the method obtains is less, and high temperature cyclic performance increases, but its filling performance is poor.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of anode material for lithium-ion batteries, its preparation method and lithium ion battery, positive electrode provided by the invention is the lithium manganese oxide with class spherical morphology, and described positive electrode has good filling capacity and high temperature cyclic performance.
The invention provides a kind of anode material for lithium-ion batteries, there is the atomic ratio composition shown in formula (I):
Li
a(M
xMn
2-x)(O
4-yZ
y)；
(I)；
Wherein, 0.8≤a≤1.2,0≤x≤1,0≤y≤1;
M is one or more in Li, Na, K, Ca, Mg, Al, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, La, Ce, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Pb and Si;
Z is one or more in OH, halogen, N, P, S and O;
The primary particle of described positive electrode has class spherical morphology, and its (111) face is connected by not having the curved surface of clear and definite rib with adjacent equivalent crystal.
Preferably, the particle diameter of the primary particle of described positive electrode is 1 μm ~ 20 μm.
Compared with prior art, anode material for lithium-ion batteries provided by the invention has the atomic ratio composition shown in formula (I), there is the crystal structure of cube spinelle (FD-3m), the primary particle of described positive electrode is that class is spherical, and its (111) face is connected by not having the curved surface of clear and definite rib with adjacent equivalent crystal.Positive electrode provided by the invention has class spherical morphology, and surface does not have clear and definite rib and sharp-pointed summit, and the angle between adjacent crystal planes is comparatively large, and therefore manganese not easily dissolves in the electrolytic solution, has good high temperature cyclic performance and filling capacity.
Present invention also offers a kind of preparation method of anode material for lithium-ion batteries, comprise the following steps:
A) will, containing manganese compound and solvent, obtain containing manganese compound solution;
What b) a) obtain to described step adds precipitation reagent containing in manganese compound solution, and be precipitated thing, described precipitation reagent is alkali-metal hydroxide solution, alkali-metal carbonate solution or alkali-metal bicarbonate solution;
C) by described step b) the sediment roasting that obtains, obtain positive electrode material precursor;
D) by described step c) roasting after the mixing of the positive electrode material precursor, MnS and the lithium-containing compound that obtain, obtain pressed powder after grinding;
E) by described steps d) pressed powder that obtains carries out annealing in process, obtains anode material for lithium-ion batteries.
Preferably, described step a) specifically comprises:
To mix in a solvent with displacer containing manganese compound, obtain containing manganese compound solution, described displacer is for containing Li compound, containing Na compound, containing K compound, containing Ca compound, containing Mg compound, containing Al compound, containing Ti compound, containing Sc compound, containing Ge compound, containing V compound, containing Cr compound, containing Zr compound, containing Co compound, containing Ni compound, containing Zn compound, containing Cu compound, containing La compound, containing Ce compound, containing Mn compound, containing Hf compound, containing Nb compound, containing Ta compound, containing Mo compound, containing W compound, containing Ru compound, containing Ag compound, containing Sn compound, containing Pb compound with containing one or more in Si compound.
Preferably, described is one or more in manganese sulfate, manganese carbonate, manganese nitrate, manganese chloride and manganese oxalate containing manganese compound.
Preferably, described solvent is water, methyl alcohol, ethanol or acetone.
Preferably, described step b) be specially:
What a) obtain to described step adds precipitation reagent, adjust ph to 6 ~ 13 containing in manganese compound solution, is precipitated thing.
Preferably, described steps d) in, described lithium-containing compound is one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride and lithium fluoride.
Preferably, described steps d) in, in described MnS and described lithium-containing compound, the mol ratio of elemental lithium is (0.001 ~ 0.1): (0.8 ~ 1.2).
Preferably, described step c) in, the temperature of described roasting is 300 DEG C ~ 800 DEG C, and the time of described roasting is 1h ~ 10h.
Preferably, described steps d) in, the temperature of described roasting is 750 DEG C ~ 1200 DEG C, and the time of described roasting is 1h ~ 48h.
Preferably, described step e) in, the temperature of described annealing is 400 DEG C ~ 800 DEG C, and the time of described annealing is 1h ~ 12h.
Present invention also offers a kind of lithium ion battery, the electrolyte comprising positive pole, negative pole and be placed between described positive pole and negative pole, it is characterized in that, described positive pole comprises the positive electrode that the positive electrode described in technique scheme or the method described in technique scheme prepare.
The present invention first will containing manganese compound or containing manganese compound and displacer and solvent, obtains, containing manganese sediment or the sediment containing manganese and substitutional element, obtaining positive electrode material precursor by after described sediment roasting after then adding precipitation reagent; Anode material for lithium-ion batteries is obtained by after the mixing of described positive electrode material precursor, MnS and lithium-containing compound, roasting, annealing.The positive electrode that method provided by the invention prepares has the crystal structure of cubic spinel (FD-3m), and main component is lithium, manganese and oxygen, is suitable for use as lithium ion cell positive.The primary particle of the lithium manganese oxygen positive electrode that method provided by the invention prepares has class spherical morphology, its (111) face with between adjacent equivalent crystal by not having the curved surface of clear and definite rib to be connected, angle between crystal plane and adjacent crystal planes is obtuse angle, class spherical structure not only filling rate is higher, and make described lithium manganese oxygen positive electrode have lower specific area, manganese element at high temperature not easily dissolves, thus improves its high temperature cyclic performance and filling capacity.Experiment shows, compared with the lithium manganese oxide of shape of octahedron, the lithium manganese oxide of class spherical morphology has lower specific area, lower manganese meltage, better high temperature cyclic performance and filling capacity.
Accompanying drawing explanation
The X ray diffracting spectrum of the lithium manganese oxygen material that Fig. 1 provides for the embodiment of the present invention 1;
The stereoscan photograph of the lithium manganese oxygen material that Fig. 2 provides for the embodiment of the present invention 1;
Fig. 3 amplifies the stereoscan photograph of 20000 times for lithium manganese oxygen material that the embodiment of the present invention 2 provides;
Fig. 4 amplifies the stereoscan photograph of 40000 times for lithium manganese oxygen material that the embodiment of the present invention 2 provides;
The stereoscan photograph of the lithium manganese oxygen material that Fig. 5 provides for comparative example 1 of the present invention;
The high temperature circulation curve of the lithium ion battery that Fig. 6 provides for the embodiment of the present invention and comparative example.
Embodiment
The invention provides a kind of anode material for lithium-ion batteries, there is the atomic ratio composition shown in formula (I):
Li
a(M
xMn
2-x)(O
4-yZ
y)；
(I)；
Wherein, 0.8≤a≤1.2,0≤x≤1,0≤y≤1;
M is one or more in Li, Na, K, Ca, Mg, Al, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, La, Ce, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Pb and Si;
Z is one or more in OH, halogen, N, P, S and O;
The primary particle of described positive electrode has class spherical morphology, and its (111) face is connected by not having the curved surface of clear and definite rib with adjacent equivalent crystal.
Positive electrode provided by the invention has the atomic ratio composition shown in formula (I), and namely the main component of described positive electrode is lithium, manganese and oxygen, wherein:
A meets the following conditions: 0.8≤a≤1.2, more preferably meets: 0.9≤a≤1.1;
X meets the following conditions: 0≤x≤1, more preferably meets: 0.01≤x≤0.5;
Y meets the following conditions: 0≤y≤1, more preferably meets: 00.1≤y≤0.5.
M is substitutional element, be preferably in Mg, Al, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, La, Ce, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Pb and Si one or more, be more preferably Mg, Al, Ti, Ge, V, Cr, Zr, Co, Ni, La, Ce or Nb;
Z is one or more in OH, halogen, N, P, S and O, is preferably halogen, N, P or S, is more preferably halogen.
Described positive electrode is lithium manganese oxide, and it has cubic spinel (FD-3m) structure, can be used as the positive electrode of lithium ion battery.
In order to make this positive electrode, there is good filling capacity, high temperature cyclic performance and low manganese to dissolve, the primary particle of described positive electrode has class spherical morphology, its (111) face is connected by not having the curved surface of clear and definite rib with adjacent equivalent crystal, namely the primary particle surface of described positive electrode does not have clear and definite rib and sharp-pointed summit, (111) angle between face and adjacent crystal planes is comparatively large.
In the present invention, described class spherical morphology, except the pattern comprising single primary particle and formed, also comprises the pattern, the primary particle crystal face that intersect to form between primary particle have the pattern of formation, primary particle superficial growth goes out other primary particles pattern, shares the pattern that crystal face formed between pattern that primary particle part defect is formed or primary particle.
In the present invention, in the primary particle of described positive electrode except there is class spherical morphology, the appearance of shape of octahedron, dodecahedron pattern or other shapes can also be had, the primary particle with class spherical morphology preferably accounts for more than 50%, be more preferably more than 80%, most preferably be more than 90%.The pattern of described positive electrode primary particle is determined by electron microscope.
The particle diameter of the primary particle of positive electrode of the present invention is preferably 1 μm ~ 20 μm, is more preferably 2 μm ~ 15 μm, most preferably is 3 μm ~ 10 μm.
Described positive electrode has lower specific area, and its specific area is preferably 0.1m
2/ g ~ 1m
2/ g, is more preferably 0.3m
2/ g ~ 0.7m
2/ g.
Described positive electrode has higher tap density, and its tap density is preferably 1.8g/cm
3~ 2.5g/cm
3, be more preferably 1.9g/cm
3~ 2.1g/cm
3.
Manganese in described positive electrode meltage is in the electrolytic solution less, and it leaves standstill after 7 days in the electrolyte of 60 DEG C, and described electrolyte is the LiPF of 1mol/L
6ethylene carbonate (EC) and dimethyl carbonate (DMC) solution, the volume ratio of EC and DMC is 1: 1, the meltage of manganese is preferably 0.001mol/L ~ 0.03mol/L, is more preferably 0.005mol/L ~ 0.025mol/L, most preferably is 0.01mol/L ~ 0.02mol/L.
Described positive electrode has good filling capacity, and after described positive electrode and acetylene black, Kynoar are prepared positive plate, its compacted density is preferably 2.50g/cm
3~ 4g/cm
3, be more preferably 2.80g/cm
3~ 3.5g/cm
3, most preferably be 2.90g/cm
3~ 3.2g/cm
3.
Positive electrode provided by the invention has class spherical morphology, and surface does not have clear and definite rib and sharp-pointed summit, and the angle between adjacent crystal planes is comparatively large, and therefore manganese not easily dissolves in the electrolytic solution, has good high temperature cyclic performance and filling capacity.
Present invention also offers a kind of preparation method of anode material for lithium-ion batteries, comprise the following steps:
A) will, containing manganese compound and solvent, obtain containing manganese compound solution;
What b) a) obtain to described step adds precipitation reagent containing in manganese compound solution, and be precipitated thing, described precipitation reagent is alkali-metal hydroxide solution, alkali-metal carbonate solution or alkali-metal bicarbonate solution;
C) by described step b) the sediment roasting that obtains, obtain positive electrode material precursor;
D) by described step c) roasting after the mixing of the positive electrode material precursor, MnS and the lithium-containing compound that obtain, obtain pressed powder after grinding;
E) by described steps d) pressed powder that obtains carries out annealing in process, obtains anode material for lithium-ion batteries.
The present invention adopts Liquid preparation methods positive electrode material precursor, and substitutional element is mixed with manganese element, thus improves the high temperature cyclic performance of positive electrode; Then being crystal face dressing agent with MnS, is the spherical lithium manganese oxygen positive electrode of class by obtaining primary particle after the mixing of MnS, positive electrode material precursor and lithium-containing compound, roasting, annealing.
First the present invention containing manganese compound and solvent, will obtain solution.
According to the present invention, described is compound containing manganese element containing manganese compound, one or more preferably in manganese sulfate, manganese carbonate, manganese nitrate, manganese chloride and manganese oxalate, is more preferably manganese sulfate, manganese nitrate or manganese chloride.
In the present invention, described solvent is preferably water, methyl alcohol, ethanol or acetone, is more preferably water.
In order to improve the performance of the positive electrode obtained, the present invention preferably prepares the positive electrode of other element dopings, namely preferably will mix in a solvent with displacer containing manganese compound, obtains containing manganese compound solution.
In the present invention, the effect of described displacer is to provide doped chemical, makes the positive electrode obtained have better high temperature cyclic performance.Described displacer can for containing Li compound, containing Na compound, containing K compound, containing Ca compound, containing Mg compound, containing Al compound, containing Ti compound, containing Sc compound, containing Ge compound, containing V compound, containing Cr compound, containing Zr compound, containing Co compound, containing Ni compound, containing Zn compound, containing Cu compound, containing La compound, containing Ce compound, containing Mn compound, containing Hf compound, containing Nb compound, containing Ta compound, containing Mo compound, containing W compound, containing Ru compound, containing Ag compound, containing Sn compound, containing Pb compound with containing one or more in Si compound, be preferably containing Li, Na, K, Ca, Mg, Al, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, La, Ce, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, the hydroxide dissolving in solvent of Pb or Si, oxide, nitride, sulfide, sulfate, chloride, fluoride, carbonate, bicarbonate, nitrate or oxalates etc., be more preferably containing Nb, V, Mg, Zr, Nu, Cr, Ti, the oxide dissolving in solvent of Al or Ce, sulfate or hydroxide.
Described when mixing in a solvent with displacer containing manganese compound, the mol ratio of manganese element and substitutional element is (2-x): x preferably, and wherein, x preferably meets the following conditions: 0≤x≤1, more preferably meets: 0.01≤x≤0.5.
Obtain, containing after manganese compound solution, adding precipitation reagent wherein, make manganese element and substitutional element generate sediment.In the present invention, described precipitation reagent is alkali-metal hydroxide solution, alkali-metal carbonate solution or alkali-metal bicarbonate solution, is preferably sodium carbonate, sodium acid carbonate, NaOH, potassium hydroxide or lithium hydroxide.
The described pH value containing manganese compound solution is preferably adjusted to 6 ~ 13 with precipitation reagent by the present invention, is more preferably 8 ~ 12.5, most preferably is 10 ~ 11.The present invention preferably drips precipitation reagent under the condition stirred, and in the process dripping precipitation reagent, hydroxyl, carbonate or the bicarbonate radical be dissolved in manganese element in solvent or substitutional element and precipitation reagent reacts generation sediment.
After being precipitated thing, by described drying precipitate, preferably dry 8h in 80 DEG C of vacuum drying ovens, carries out roasting by dried sediment, obtains positive electrode material precursor.Described sediment is preferably carried out roasting by the present invention in tube furnace, and during roasting, the flow velocity of oxygen is preferably 1mL/min ~ 5mL/min, is more preferably 2mL/min ~ 4mL/min.The temperature of described roasting is preferably 300 DEG C ~ 800 DEG C, is more preferably 400 DEG C ~ 600 DEG C; The time of described roasting is preferably 1h ~ 10h, is more preferably 2h ~ 6h.
After roasting, obtain the compound containing manganese, substitutional element and oxygen, obtain positive electrode material precursor by after described compound cooling, grinding.Different according to the raw material selected, containing manganese, oxygen, substitutional element or halogen, N, P, S etc. in described positive electrode material precursor.
After obtaining positive electrode material precursor, with this positive electrode material precursor for anode material for lithium-ion batteries prepared by raw material.First described positive electrode material precursor, MnS and lithium-containing compound are mixed, after then carrying out roasting, annealing, obtain positive electrode.
In the present invention, described MnS is crystal face dressing agent, namely modifies the crystal shape of the positive electrode obtained, obtains spherical crystal.In described MnS and described lithium-containing compound, the mol ratio of elemental lithium is preferably (0.001 ~ 0.1): (0.8 ~ 1.2), be more preferably (0.005 ~ 0.08): (0.9 ~ 1.1), most preferably be (0.01 ~ 0.05): (0.95 ~ 1.05).
In the present invention, described lithium-containing compound is the compound containing elemental lithium, is preferably one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride and lithium fluoride, is more preferably lithium hydroxide or lithium carbonate.In the molal quantity of described lithium-containing compound and described positive electrode, the ratio of the total mole number of manganese element and substitutional element is preferably (0.8 ~ 1.2): 2, be more preferably (0.9 ~ 1.1): 2, most preferably be (0.95 ~ 1.05): 2.
The present invention preferably by described positive electrode material precursor, MnS and lithium-containing compound in batch mixer, add batch mixing ball and mix, the weight of described batch mixing ball is preferably 2 times of positive electrode material precursor, MnS and lithium-containing compound total weight.
In resistance furnace, carry out roasting after described positive electrode material precursor, MnS and lithium-containing compound being mixed, the temperature of described roasting is preferably 750 DEG C ~ 1200 DEG C, is more preferably 800 DEG C ~ 1100 DEG C, most preferably is 900 DEG C ~ 1000 DEG C; The time of described roasting is preferably 1h ~ 48h, is more preferably 5h ~ 30h, most preferably is 8h ~ 16h.Sintering temperature has considerable influence to the formation of spherical crystal and performance thereof, the positive electrode crystal structure obtained under the condition of high temperature is comparatively regular, when sintering temperature is too low, in the crystal of formation, spherical crystal content is low, and the high temperature cyclic performance of the material obtained is bad.
After roasting, the sintered body obtained is cooled to room temperature, grinds to form pressed powder, then the pressed powder obtained is annealed, be warming up to annealing temperature by described pressed powder, after the cooling of insulation a period of time, obtain positive electrode.
Described pressed powder is preferably annealed by the present invention in resistance furnace, and described annealing temperature is preferably 400 DEG C ~ 800 DEG C, is more preferably 500 DEG C ~ 700 DEG C, most preferably is 550 DEG C ~ 650 DEG C; Described annealing time is preferably 1h ~ 12h, is more preferably 2h ~ 6h, most preferably is 3h ~ 5h.Annealing in process makes the positive electrode obtained have better class spherical morphology, has better filling capacity and high temperature cyclic performance.
After obtaining anode material for lithium-ion batteries, carry out X-ray diffraction analysis to described positive electrode, result proves its positive spinel with standard (FD-3M) cubic structure, and free from admixture phase, illustrate that it can be used as anode material for lithium-ion batteries.
After obtaining anode material for lithium-ion batteries, carry out electron microscopic observation to it, result shows, the anode material for lithium-ion batteries adopting method provided by the invention to prepare is spherical crystal, it does not have clear and definite corner angle, and the angle between crystal plane and adjacent crystal planes is obtuse angle.Because manganese dissolving in the electrolytic solution mainly occurs in the large place of particle curvature, namely occur in rib and sharp-pointed summit, the positive electrode prepared due to the present invention does not have rib and sharp-pointed summit substantially, and therefore, manganese dissolving in the electrolytic solution reduces greatly.
In the positive electrode that method provided by the invention prepares, the content of spherical crystal is more than 50%, and major part is more than 90%.In the present invention, class spherical comprises the form, the crystal plane that intersect to form between primary particle and to have or the superficial growth of primary particle goes out the form etc. being shared formation between the form of other primary particles, the form of primary particle segmental defect or primary particle by complicated crystal plane.
Positive electrode the present invention prepared is placed in electrolyte, and in 60 DEG C of baking ovens, place the meltage measuring its manganese for 7 days afterwards, experiment shows, the meltage of manganese is lower in the electrolytic solution under the high temperature conditions for positive electrode prepared by the present invention.
Measure the tap density of the positive electrode that the present invention prepares, and positive electrode the present invention prepared and acetylene black, Kynoar and N-first class pyrrolidones are mixed with and obtain positive plate, and measure the compacted density of positive plate, result shows, positive electrode prepared by the present invention has good filling capacity.
Present invention also offers a kind of lithium ion battery, the electrolyte comprising positive pole, negative pole and be placed between described positive pole and negative pole, the positive electrode that described positive pole is comprised the positive electrode described in technique scheme or prepared by the method described in technique scheme.
In described lithium ion battery, the positive electrode that described positive pole is comprised the positive electrode described in technique scheme or prepared by the method described in technique scheme, also comprises the conventional material such as acetylene black, Kynoar.Described positive pole is preferably prepared in accordance with the following methods:
Positive electrode described in technique scheme or the positive electrode, acetylene black, Kynoar and the solvent that are prepared by the method described in technique scheme are obtained slurry;
Described slurry is coated in aluminium foil surface, after compression, obtains positive pole.
The negative pole of the present invention to described lithium ion battery is not particularly limited, and can be lithium, silicon or lithium alloy etc., also can be the carbon element compounds that the reversible absorption such as graphite release lithium ion.
The electrolyte of the present invention to described lithium ion battery is not particularly limited, and can be liquid electrolyte, also can be organic solid electrolyte based or inorganic solid electrolyte, is preferably liquid electrolyte; When described electrolyte is liquid electrolyte, described electrolyte can be LiClO
4, LiPF
6, LiBF
4, at least one in the lithium salts such as trifluoromethayl sulfonic acid lithium, be preferably LiPF
6; Solvent can be the carbonic ester such as propylene carbonate, carbonic acid dihexyl, also can be the ether compound such as the sulfolane such as sulfolane, dimethyl sulfoxide (DMSO) or dimethoxy-ethane, being preferably volume ratio be the ethylene carbonate (EC) of 1: 1 and the mixed solution of dimethyl carbonate (DMC).
Described positive pole, electrolyte and negative pole are assembled according to method well known in the art, can lithium ion battery be obtained.
After obtaining lithium ion battery, adopt high temperature test instrument to carry out high temperature cyclic performance test to it, result surface, lithium ion battery provided by the invention has good high temperature cyclic performance at 60 DEG C of temperature.
The present invention first will containing manganese compound or containing manganese compound and displacer and solvent, obtains, containing manganese sediment or the sediment containing manganese and substitutional element, obtaining positive electrode material precursor by after described sediment roasting after then adding precipitation reagent; Anode material for lithium-ion batteries is obtained by after the mixing of described positive electrode material precursor, MnS and lithium-containing compound, roasting, annealing.The positive electrode that method provided by the invention prepares has cubic spinel (FD-3m) structure, and main component is lithium, manganese and oxygen, is suitable for use as lithium ion cell positive.The primary particle of the lithium manganese oxygen positive electrode that method provided by the invention prepares is spherical crystal, by not having the curved surface of clear and definite rib to be connected between its crystal plane with adjacent crystal planes, angle between crystal plane and adjacent crystal planes is obtuse angle, class spherical structure not only filling rate is higher, and make described lithium manganese oxygen positive electrode have lower specific area, manganese element at high temperature not easily dissolves, thus improves its high temperature cyclic performance and filling capacity.
In order to further illustrate the present invention, below in conjunction with embodiment, anode material for lithium-ion batteries provided by the invention, its preparation method and lithium ion battery are described in detail.
Embodiment 1 ~ 10
According to the raw material shown in table 1, consumption and condition, prepare lithium manganese oxygen material precursor according to following steps:
Add displacer to containing in the solution of manganese compound, under the condition of stirring, slowly drip precipitation reagent, regulate the pH value of the mixed solution obtained, after filtration, obtain mixed sediment; By described mixed sediment at vacuum, dry 8h at 80 DEG C, be the tubular type kiln roasting of 2mL/min at oxygen gas flow rate by dried mixed sediment, obtain the presoma of lithium manganese oxygen material.
Table 1 embodiment of the present invention 1 ~ 10 prepares formula and the condition of lithium manganese oxygen material precursor
According to the raw material shown in table 2, consumption and condition, prepare lithium manganese oxygen material according to following steps:
The presoma of described lithium manganese oxygen, lithium-containing compound and crystal face dressing agent MnS are put into batch mixer, add the batch mixing ball mixing that weight is lithium manganese oxygen presoma, lithium salts and crystal face dressing agent total weight 2 times, by the mixed material roasting obtained, be cooled to room temperature, grind, sieve after anneal, obtain lithium manganese oxygen material after being cooled to room temperature.
Table 2 embodiment of the present invention 1 ~ 10 prepares formula and the condition of lithium manganese oxygen material
The polycrystalline diffractometer of German Brooker company is used to carry out X-ray diffraction analysis to lithium manganese oxygen material prepared by each embodiment, with CuK α line for light source, the angle of diffraction 2 θ is from 10 ° to 90 °, result is see Fig. 1, the X ray diffracting spectrum of the lithium manganese oxygen material that Fig. 1 provides for the embodiment of the present invention 1, as shown in Figure 1, the lithium manganese oxygen material that the embodiment of the present invention 1 prepares has positive spinel (FD-3M) cubic structure of standard, and free from admixture phase.The lithium manganese oxygen material that embodiment 2 ~ 10 prepares all has positive spinel (FD-3M) cubic structure of standard, and free from admixture phase.
Electron-microscope scanning is carried out to described lithium manganese oxygen material, result is see Fig. 2, Fig. 3 and Fig. 4, the stereoscan photograph of the lithium manganese oxygen material that Fig. 2 provides for the embodiment of the present invention 1, Fig. 3 amplifies the stereoscan photograph of 20000 times for lithium manganese oxygen material that the embodiment of the present invention 2 provides, Fig. 4 amplifies the stereoscan photograph of 40000 times for lithium manganese oxygen material that the embodiment of the present invention 2 provides, by Fig. 2, Fig. 3 and Fig. 4 is known, the lithium manganese oxygen material that the present invention prepares is spherical crystal structure, there is no clear and definite corner angle, angle between crystal plane and adjacent crystal planes is obtuse angle, and angle trends towards 0.
Carry out performance test to described lithium manganese oxygen material, result is see table 3, and table 3 is the performance parameter of lithium manganese oxygen material prepared by the embodiment of the present invention and comparative example.
The LiPF of 1mol/L is loaded in 100mL volumetric flask
6ethylene carbonate (EC) and dimethyl carbonate (DMC) solution, wherein, the volume ratio of EC and DMC is 1: 1, then lithium manganese oxygen material prepared by each embodiment of 2g is added, place after described volumetric flask sealing 7 days in 60 DEG C of baking ovens, with centrifuge removing lithium manganese oxygen material, collect solution; The Optima2100 type Inductively coupled plasma optical emission spectrometer of use Perkin-Elmer company tests the Fe content in described solution, and result is see table 4, and the manganese that table 4 provides for the embodiment of the present invention and comparative example dissolves test experiments result.
Lithium manganese oxygen material, 1g acetylene black, 1g Kynoar and the 30gN-methyl pyrrolidone each for 8g embodiment prepared are mixed to form slurry at normal temperatures and pressures, are evenly coated in aluminium foil surface and obtain pole piece; Compress after described pole piece is dried at 80 DEG C, obtain positive plate; Roll squeezer is used to carry out roll-in to described positive plate, measure with the thickness of micrometer caliper to positive plate, record the thickness before positive plate roll-in and after roll-in respectively, calculate compacted density, result see table 5, the filling capacity test result of the lithium manganese oxygen material that table 5 provides for the embodiment of the present invention and comparative example.
Comparative example 1
9.7g electrolytic manganese dioxide, 0.49g aluminium hydroxide, 2.66g lithium hydroxide are put into batch mixer, add the batch mixing ball mixing of 2 times of weight, by the mixed material that the obtains resistance kiln roasting 20h at 950 DEG C, be cooled to room temperature, grind, sieve after continue at 550 DEG C resistance kiln roasting 10h, obtain lithium manganese oxygen material after being cooled to room temperature, described lithium manganese oxygen material has following atomic ratio: Li
1.05al
0.1mn
1.85o
4.
Electron-microscope scanning is carried out to described lithium manganese oxygen material, the stereoscan photograph of the lithium manganese oxygen material that result provides for comparative example 1 of the present invention see Fig. 5, Fig. 5, as shown in Figure 5, the lithium manganese oxygen material that comparative example 1 prepares is octahedra shape, has sharp-pointed rib and summit.
Carry out performance test to described lithium manganese oxygen material, result is see table 3, and table 3 is the performance parameter of lithium manganese oxygen material prepared by the embodiment of the present invention and comparative example.
The performance parameter of lithium manganese oxygen material prepared by table 3 embodiment of the present invention and comparative example
As shown in Table 3, the lithium manganese oxygen material that the embodiment of the present invention provides has higher tap density, lower specific area and less primary particle average grain diameter.
The LiPF of 1mol/L is loaded in 100mL volumetric flask
6ethylene carbonate (EC) and dimethyl carbonate (DMC) solution, wherein, the volume ratio of EC and DMC is 1: 1, then lithium manganese oxygen material described in 2g is added, place after described volumetric flask sealing 7 days in 60 DEG C of baking ovens, with centrifuge removing lithium manganese oxygen material, collect solution; The Optima2100 type Inductively coupled plasma optical emission spectrometer of use Perkin-Elmer company tests manganese 4 content in described solution, and result is see table 4, and the manganese 4 that table 4 provides for the embodiment of the present invention and comparative example dissolves test experiments result.
The manganese 4 that table 4 embodiment of the present invention and comparative example provide dissolves test experiments result
As shown in Table 4, in the class spherical lithium manganese oxygen material prepared of the embodiment of the present invention, the dissolving of manganese is less than the lithium manganese oxygen material of octahedra shape.
Lithium manganese oxygen material, 1g acetylene black, 1g Kynoar and 30gN-methyl pyrrolidone described in 8g are mixed to form slurry at normal temperatures and pressures, are evenly coated in aluminium foil surface and obtain pole piece; Compress after described pole piece is dried at 80 DEG C, obtain positive plate; Roll squeezer is used to carry out roll-in to described positive plate, measure with the thickness of micrometer caliper to positive plate, record the thickness before positive plate roll-in and after roll-in respectively, calculate compacted density, result see table 5, the filling capacity test result of the lithium manganese oxygen material that table 5 provides for the embodiment of the present invention and comparative example.
The filling capacity test result of the lithium manganese oxygen material that table 5 embodiment of the present invention and comparative example provide
As shown in Table 5, the filling capacity of class spherical lithium manganese oxygen material that prepared by the embodiment of the present invention is better than octahedra shape lithium manganese oxygen material prepared by comparative example 1.
Embodiment 11
Lithium manganese oxygen material, 1g acetylene black, 1g Kynoar and the 30gN-methyl pyrrolidone 8g embodiment 1 prepared are mixed to form slurry at normal temperatures and pressures, are evenly coated in aluminium foil surface and obtain pole piece; Compress after being dried at 80 DEG C by described pole piece, being cut into area is 1.32cm
2thin rounded flakes as positive pole, take pour lithium slice as negative pole, with the LiPF of 1mol/L
6ethylene carbonate (EC) and dimethyl carbonate (DMC) solution be electrolyte, wherein, the volume ratio of EC and DMC is 1: 1, in the glove box being full of argon gas, be assembled into lithium ion battery.
Use high temperature test instrument to carry out cycle performance test to described lithium ion battery, probe temperature is 60 DEG C, and charging and discharging currents is 0.4mA/cm
2charging grafting voltage is 4.35V, discharge cut-off voltage is 3.0V, result is see Fig. 6, the high temperature circulation curve of the lithium ion battery that Fig. 6 provides for the embodiment of the present invention and comparative example, wherein, the high temperature circulation curve of the lithium ion battery that curve 1 provides for the embodiment of the present invention 11, the high temperature circulation curve of the lithium ion battery that curve 2 provides for comparative example 2 of the present invention.
Comparative example 2
Lithium manganese oxygen material, 1g acetylene black, 1g Kynoar and the 30gN-methyl pyrrolidone prepared by 8g comparative example 1 are mixed to form slurry at normal temperatures and pressures, are evenly coated in aluminium foil surface and obtain pole piece; Compress after being dried at 80 DEG C by described pole piece, being cut into area is 1.32cm
2thin rounded flakes as positive pole, take pour lithium slice as negative pole, with the LiPF of 1mol/L
6ethylene carbonate (EC) and dimethyl carbonate (DMC) solution be electrolyte, wherein, the volume ratio of EC and DMC is 1: 1, in the glove box being full of argon gas, be assembled into lithium ion battery.
Use high temperature test instrument to carry out cycle performance test to described lithium ion battery, probe temperature is 60 DEG C, and charging and discharging currents is 0.4mA/cm
2charge by voltage be 4.3V, discharge cut-off voltage is 3.0V, result is see Fig. 6, the high temperature circulation curve of the lithium ion battery that Fig. 6 provides for the embodiment of the present invention and comparative example, wherein, the high temperature circulation curve of the lithium ion battery that curve 1 provides for the embodiment of the present invention 11, the high temperature circulation curve of the lithium ion battery that curve 2 provides for comparative example 2 of the present invention.As shown in Figure 6, the high temperature cyclic performance of lithium ion battery that the embodiment of the present invention provides is better than the high temperature cyclic performance of the lithium ion battery that comparative example 2 provides.
From above-described embodiment and comparative example, method provided by the invention can prepare the lithium manganese oxygen material of class spherical structure, and it has good high temperature cyclic performance and filling capacity.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (12)
1. an anode material for lithium-ion batteries, has the atomic ratio composition shown in formula (I):
Li
a(M
xMn
2-x)(O
4-yZ
y)；
(I)；
Wherein, 0.8≤a≤1.2,0≤x≤1,0≤y≤1;
M is one or more in Li, Na, K, Ca, Mg, Al, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, La, Ce, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Pb and Si;
Z is one or more in OH, halogen, N, P, S and O;
The primary particle of described positive electrode has class spherical morphology, and its (111) face is connected by not having the curved surface of clear and definite rib with adjacent equivalent crystal; Angle between crystal plane and adjacent crystal planes is obtuse angle.
2. anode material for lithium-ion batteries according to claim 1, is characterized in that, the particle diameter of the primary particle of described positive electrode is 1 μm ~ 20 μm.
3. a preparation method for anode material for lithium-ion batteries, comprises the following steps:
A) will, containing manganese compound and solvent, obtain containing manganese compound solution;
What b) a) obtain to described step adds precipitation reagent containing in manganese compound solution, and be precipitated thing, described precipitation reagent is alkali-metal hydroxide solution, alkali-metal carbonate solution or alkali-metal bicarbonate solution;
C) by described step b) the sediment roasting that obtains, obtain positive electrode material precursor;
D) by described step c) roasting after the mixing of the positive electrode material precursor, MnS and the lithium-containing compound that obtain, obtain pressed powder after grinding; In described MnS and described lithium-containing compound, the mol ratio of elemental lithium is (0.001 ~ 0.1): (0.8 ~ 1.2);
E) by described steps d) pressed powder that obtains carries out annealing in process, obtains anode material for lithium-ion batteries.
4. preparation method according to claim 3, is characterized in that, described step a) specifically comprises:
To mix in a solvent with displacer containing manganese compound, obtain containing manganese compound solution, described displacer is for containing Li compound, containing Na compound, containing K compound, containing Ca compound, containing Mg compound, containing Al compound, containing Ti compound, containing Sc compound, containing Ge compound, containing V compound, containing Cr compound, containing Zr compound, containing Co compound, containing Ni compound, containing Zn compound, containing Cu compound, containing La compound, containing Ce compound, containing Mn compound, containing Hf compound, containing Nb compound, containing Ta compound, containing Mo compound, containing W compound, containing Ru compound, containing Ag compound, containing Sn compound, containing Pb compound with containing one or more in Si compound.
5. preparation method according to claim 4, is characterized in that, described is one or more in manganese sulfate, manganese carbonate, manganese nitrate, manganese chloride and manganese oxalate containing manganese compound.
6. preparation method according to claim 4, is characterized in that, described solvent is water, methyl alcohol, ethanol or acetone.
7. preparation method according to claim 3, is characterized in that, described step b) be specially:
What a) obtain to described step adds precipitation reagent, adjust ph to 6 ~ 13 containing in manganese compound solution, is precipitated thing.
8. preparation method according to claim 3, is characterized in that, described steps d) in, described lithium-containing compound is one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride and lithium fluoride.
9. the preparation method according to claim 3 ~ 8 any one, is characterized in that, described step c) in, the temperature of described roasting is 300 DEG C ~ 800 DEG C, and the time of described roasting is 1h ~ 10h.
10. the preparation method according to claim 3 ~ 8 any one, is characterized in that, described steps d) in, the temperature of described roasting is 750 DEG C ~ 1200 DEG C, and the time of described roasting is 1h ~ 48h.
11. preparation methods according to claim 3 ~ 8 any one, is characterized in that, described step e) in, the temperature of described annealing is 400 DEG C ~ 800 DEG C, and the time of described annealing is 1h ~ 12h.
12. 1 kinds of lithium ion batteries, the electrolyte comprising positive pole, negative pole and be placed between described positive pole and negative pole, it is characterized in that, the positive electrode that described positive pole is comprised the positive electrode described in claim 1 or 2 or prepared by the method described in claim 3 ~ 11 any one.
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| CN114613985A (en) * | 2022-03-07 | 2022-06-10 | 宁波容百新能源科技股份有限公司 | High-voltage nickel-manganese material with high single crystal dispersibility as well as preparation method and application thereof |
| WO2024050758A1 (en) * | 2022-09-08 | 2024-03-14 | 宁德时代新能源科技股份有限公司 | Lithium-containing nickel-manganese composite oxide, preparation method therefor, and positive pole piece, secondary battery and electric device comprising same |
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