CN102800840A - 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, relate in particular 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, mainly relies on lithium ion between positive pole and negative pole, to move and realizes discharging and recharging.Lithium ion battery has that fail safe is good, voltage and specific energy are high, discharge and recharge advantages such as the life-span is long, thereby is 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, like lithium cobalt oxygen, LiFePO4, lithium manganese oxygen etc., wherein; Lithium cobalt oxygen has advantages such as high power capacity, high voltage, easy preparation, but cobalt costs an arm and a leg and can produce harm to environment; Advantage such as that LiFePO4 has is safe, have extended cycle life, but its electrode processing characteristics is bad, consistency is poor; Lithium manganese oxygen is a kind of material with three-dimensional lithium ion passage, has that price is low, current potential is high, an environmental friendliness, security performance advantages of higher, and lithium manganese oxygen material is adapted at the application of large energy accumulation battery aspect such as electric motor car, thereby becomes one of research focus.But, be the shortcoming that the lithium ion battery of positive pole has the high temperature cyclic performance difference with lithium manganese oxygen, limited its further application.
Existing research it is generally acknowledged that the specific area of lithium manganese oxygen is one of key factor that influences the lithium ion battery high temperature cyclic performance; Low specific area can reduce contacting of lithium manganese oxygen material and electrolyte; Thereby reduce the dissolving of manganese, improve the high temperature cyclic performance of lithium ion battery.At present generally adopt oxide or fluoride coats lithium manganese oxygen material or the method for other element high temperature sinterings that mix obtains the lithium manganese oxygen of low specific surface area.Like publication number is that the Chinese patent document of CN1787254 discloses a kind of anode material for lithium-ion batteries; At first soluble metallic salt is dissolved in the solvent; Add the spinel lithium manganate or derivatives thereof then and form suspension-turbid liquid; With roasting behind the said suspension-turbid liquid spray drying granulation, obtain the spinel lithium manganate that the surface is coated with metal oxide, though coat the high-temperature behavior that to improve lithium manganese oxygen material to a certain extent; Increase the production stage of spinel lithium manganate but coat, and be difficult to guarantee consistency of product.
Publication number is that the Chinese patent document of CN1455466 discloses a kind of constitutionally stable spinel lithium manganate; Obtain by electrolytic manganese dioxide, lithium carbonate, cobalt oxide with by the multi-element doping body roasting at high temperature that nickel, chromium, iron, manganese, selenium and fluorine are formed; This method has improved the cycle performance of LiMn2O4, but its high temperature cyclic performance is still lower.Publication number is that the Chinese patent document of CN101587950 discloses the LiMn2O4 that a kind of micron order regular octahedron monocrystalline is formed, through roasting after the composite oxides of manganese and modified metal M and the lithium salts ball mill mixing is obtained.The lithium manganese oxygen material specific area that this method obtains is less, and high temperature cyclic performance increases, but its filling performance is relatively poor.
Summary of the invention
In view of this; The technical problem that the present invention will solve 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 and oxygen compound of type of having spherical morphology, and said positive electrode has good filling property ability and high temperature cyclic performance.
The invention provides a kind of anode material for lithium-ion batteries, have the atomic ratio shown in the formula (I) and form:
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 among 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 the Si;
Z is one or more among OH, halogen, N, P, S and the O;
Primary particle type of the having spherical morphology of said positive electrode, its (111) face is connected through the curved surface that does not have clear and definite rib with adjacent equivalent crystal.
Preferably, the particle diameter of the primary particle of said positive electrode is 1 μ m～20 μ m.
Compared with prior art; Anode material for lithium-ion batteries provided by the invention has the atomic ratio shown in the formula (I) and forms; Crystal structure with cube spinelle (FD-3m); Primary particle type of being of said positive electrode is spherical, and its (111) face is connected through the curved surface that does not have clear and definite rib with adjacent equivalent crystal.Positive electrode type of having spherical morphology provided by the invention, the surface does not have clear and definite rib and sharp-pointed summit, and the angle between the phase vicinal face is bigger, and therefore manganese is difficult for dissolving in electrolyte, has good high-temperature cycle performance and filling capacity.
The present invention also provides a kind of preparation method of anode material for lithium-ion batteries, may further comprise the steps:
A) will contain manganese compound and solvent, obtain containing manganese compound solution;
B) containing in the manganese compound solution of obtaining add precipitation reagent to said step a), obtain sediment, said precipitation reagent is alkali-metal hydroxide solution, alkali-metal carbonate solution or alkali-metal bicarbonate solution;
C) the sediment roasting that said step b) is obtained obtains the positive electrode presoma;
D) the positive electrode presoma that said step c) is obtained, MnS and lithium-containing compound mix the back roasting, obtain pressed powder after the grinding;
E) pressed powder that said step d) is obtained carries out annealing in process, obtains anode material for lithium-ion batteries.
Preferably, said step a) specifically comprises:
To contain manganese compound mixes in solvent with displacer; Obtain containing manganese compound solution, said displacer is to contain the Li compound, contain the Na compound, contain the K compound, contain the Ca compound, contain the Mg compound, contain the Al compound, contain the Ti compound, contain the Sc compound, contain the Ge compound, contain the V compound, contain the Cr compound, contain the Zr compound, contain the Co compound, contain the Ni compound, contain the Zn compound, contain the Cu compound, contain the La compound, contain the Ce compound, contain the Mn compound, contain the Hf compound, contain the Nb compound, contain the Ta compound, contain the Mo compound, contain the W compound, contain the Ru compound, contain the Ag compound, contain the Sn compound, contain the Pb compound and contain in the Si compound one or more.
Preferably, the said manganese compound that contains is in manganese sulfate, manganese carbonate, manganese nitrate, manganese chloride and the manganese oxalate one or more.
Preferably, said solvent is water, methyl alcohol, ethanol or acetone.
Preferably, said step b) is specially:
Containing in the manganese compound solution of obtaining add precipitation reagent to said step a), regulate pH value to 6～13, obtain sediment.
Preferably, in the said step d), said lithium-containing compound is one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride and the lithium fluoride.
Preferably, in the said step d), the mol ratio of elemental lithium is (0.001～0.1) in said MnS and the said lithium-containing compound: (0.8～1.2).
Preferably, in the said step c), the temperature of said roasting is 300 ℃～800 ℃, and the time of said roasting is 1h～10h.
Preferably, in the said step d), the temperature of said roasting is 750 ℃～1200 ℃, and the time of said roasting is 1h～48h.
Preferably, in the said step e), the temperature of said annealing is 400 ℃～800 ℃, and the time of said annealing is 1h～12h.
The present invention also provides a kind of lithium ion battery; Comprise positive pole, negative pole and place the electrolyte between said positive pole and the negative pole; It is characterized in that said positive pole comprises the positive electrode that described positive electrode of technique scheme or the described method of technique scheme prepare.
The present invention at first will contain manganese compound or contain manganese compound and displacer and solvent, obtain containing the manganese sediment or will contain manganese and the sediment of substitutional element after adding precipitation reagent then, with obtaining the positive electrode presoma after the said sediment roasting; With obtaining anode material for lithium-ion batteries after said positive electrode presoma, MnS and lithium-containing compound mixing, roasting, the 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 as lithium ion cell positive.Primary particle type of the having spherical morphology of the lithium manganese oxygen positive electrode that method provided by the invention prepares; Link to each other through the curved surface that does not have clear and definite rib between its (111) face and the adjacent equivalent crystal; Crystal plane is the obtuse angle with the angle between the vicinal face mutually, and not only filling rate is higher for a type spherical structure, and makes said lithium manganese oxygen positive electrode have lower specific area; Manganese element at high temperature is difficult for dissolving, thereby has improved its high temperature cyclic performance and filling capacity.Experiment shows, compares with the lithium manganese and oxygen compound of shape of octahedron, and the lithium manganese and oxygen compound of type spherical morphology has lower specific area, lower manganese meltage, better high temperature cyclic performance and filling capacity.
Description of drawings
The X ray diffracting spectrum of the lithium manganese oxygen material that Fig. 1 provides for the embodiment of the invention 1;
The stereoscan photograph of the lithium manganese oxygen material that Fig. 2 provides for the embodiment of the invention 1;
The lithium manganese oxygen material that Fig. 3 provides for the embodiment of the invention 2 amplifies 20000 times stereoscan photograph;
The lithium manganese oxygen material that Fig. 4 provides for the embodiment of the invention 2 amplifies 40000 times stereoscan photograph;
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 invention and comparative example.
Embodiment
The invention provides a kind of anode material for lithium-ion batteries, have the atomic ratio shown in the formula (I) and form:
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 among 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 the Si;
Z is one or more among OH, halogen, N, P, S and the O;
Primary particle type of the having spherical morphology of said positive electrode, its (111) face is connected through the curved surface that does not have clear and definite rib with adjacent equivalent crystal.
Positive electrode provided by the invention has the atomic ratio shown in the formula (I) to be formed, and promptly the main component of said positive electrode is lithium, manganese and oxygen, wherein:
A meets the following conditions: 0.8≤a≤1.2, more preferably satisfy: 0.9≤a≤1.1;
X meets the following conditions: 0≤x≤1, more preferably satisfy: 0.01≤x≤0.5;
Y meets the following conditions: 0≤y≤1, more preferably satisfy: 00.1≤y≤0.5.
M is a substitutional element; Be preferably among 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 the Si one or more, more preferably Mg, Al, Ti, Ge, V, Cr, Zr, Co, Ni, La, Ce or Nb;
Z is one or more among OH, halogen, N, P, S and the O, is preferably halogen, N, P or S, more preferably halogen.
Said positive electrode is the lithium manganese and oxygen compound, 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 have good filling property ability, high temperature cyclic performance and low manganese dissolving; Primary particle type of the having spherical morphology of said positive electrode; Its (111) face is connected through the curved surface that does not have clear and definite rib with adjacent equivalent crystal; The primary particle surface that is said positive electrode does not have clear and definite rib and sharp-pointed summit, and the angle between (111) face and the phase vicinal face is bigger.
In the present invention; Said type spherical morphology also comprises the pattern that shared crystal face forms between pattern or the primary particle of the total pattern that forms of pattern, primary particle crystal face that intersects to form between the primary particle, pattern that the primary particle superficial growth goes out other primary particles, the damaged formation of a primary particle part except the pattern that comprises single primary particle and form.
In the present invention; In the primary particle of said positive electrode except type of having spherical morphology; The appearance that can also have shape of octahedron, dodecahedron pattern or other shapes; The primary particle of type of having spherical morphology preferably accounts for more than 50%, more preferably more than 80%, most preferably is more than 90%.The pattern of said positive electrode primary particle can be confirmed through electron microscope.
The particle diameter of the primary particle of positive electrode of the present invention is preferably 1 μ m～20 μ m, and more preferably 2 μ m～15 μ m most preferably are 3 μ m～10 μ m.
Said positive electrode has lower specific area, and its specific area is preferably 0.1m
2/ g～1m
2/ g, more preferably 0.3m
2/ g～0.7m
2/ g.
Said positive electrode has higher tap density, and its tap density is preferably 1.8g/cm
3～2.5g/cm
3, 1.9g/cm more preferably
3～2.1g/cm
3
The meltage of manganese in the said positive electrode in electrolyte is less, and it leaves standstill 7 days in 60 ℃ electrolyte after, said 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, more preferably 0.005mol/L～0.025mol/L most preferably is 0.01mol/L～0.02mol/L.
Said positive electrode have good filling property can, said positive electrode and acetylene black, Kynoar prepared positive plate after, its compacted density is preferably 2.50g/cm
3～4g/cm
3, 2.80g/cm more preferably
3～3.5g/cm
3, most preferably be 2.90g/cm
3～3.2g/cm
3
Positive electrode type of having spherical morphology provided by the invention, the surface does not have clear and definite rib and sharp-pointed summit, and the angle between the phase vicinal face is bigger, and therefore manganese is difficult for dissolving in electrolyte, has good high-temperature cycle performance and filling capacity.
The present invention also provides a kind of preparation method of anode material for lithium-ion batteries, may further comprise the steps:
A) will contain manganese compound and solvent, obtain containing manganese compound solution;
B) containing in the manganese compound solution of obtaining add precipitation reagent to said step a), obtain sediment, said precipitation reagent is alkali-metal hydroxide solution, alkali-metal carbonate solution or alkali-metal bicarbonate solution;
C) the sediment roasting that said step b) is obtained obtains the positive electrode presoma;
D) the positive electrode presoma that said step c) is obtained, MnS and lithium-containing compound mix the back roasting, obtain pressed powder after the grinding;
E) pressed powder that said step d) is obtained carries out annealing in process, obtains anode material for lithium-ion batteries.
The present invention adopts liquid phase method to prepare the positive electrode presoma, and substitutional element and manganese element are mixed, thereby improves the high temperature cyclic performance of positive electrode; Be the crystal face dressing agent then with MnS, be a type spherical lithium manganese oxygen positive electrode obtaining primary particle after MnS, positive electrode presoma and lithium-containing compound mixing, roasting, the annealing.
The present invention at first will contain manganese compound and solvent, obtain solution.
According to the present invention, the said manganese compound that contains is the compound that contains manganese element, is preferably in manganese sulfate, manganese carbonate, manganese nitrate, manganese chloride and the manganese oxalate one or more, more preferably manganese sulfate, manganese nitrate or manganese chloride.
In the present invention, said solvent is preferably water, methyl alcohol, ethanol or acetone, more preferably water.
In order to improve the performance of the positive electrode that obtains, the positive electrode of other element dopings of preferred for preparation of the present invention promptly preferably will contain manganese compound and mix in solvent with displacer, obtain containing manganese compound solution.
In the present invention, the effect of said displacer is to provide doped chemical, makes the positive electrode that obtains have better high temperature cyclic performance.Said displacer can be for containing the Li compound, contain the Na compound, contain the K compound, contain the Ca compound, contain the Mg compound, contain the Al compound, contain the Ti compound, contain the Sc compound, contain the Ge compound, contain the V compound, contain the Cr compound, contain the Zr compound, contain the Co compound, contain the Ni compound, contain the Zn compound, contain the Cu compound, contain the La compound, contain the Ce compound, contain the Mn compound, contain the Hf compound, contain the Nb compound, contain the Ta compound, contain the Mo compound, contain the W compound, contain the Ru compound, contain the Ag compound, contain the Sn compound, contain the Pb compound and containing in the Si compound one or more; Be preferably the hydroxide that dissolves in solvent, oxide, nitride, sulfide, sulfate, chloride, fluoride, carbonate, bicarbonate, nitrate or the oxalates etc. that contain 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 or Si, more preferably contain the oxide that dissolves in solvent, sulfate or the hydroxide of Nb, V, Mg, Zr, Nu, Cr, Ti, Al or Ce.
Said when containing manganese compound and mixing in solvent with displacer, the mol ratio of manganese element and substitutional element is preferably (2-x): x, and wherein, x preferably meets the following conditions: 0≤x≤1, more preferably satisfy: 0.01≤x≤0.5.
After obtaining containing manganese compound solution,, make manganese element and substitutional element generate sediment to wherein adding precipitation reagent.In the present invention, said 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 present invention preferably is adjusted to 6～13 with precipitation reagent with the said pH value that contains manganese compound solution, and more preferably 8～12.5, most preferably be 10～11.The present invention preferably drips precipitation reagent under stirring condition, in dripping the process of precipitation reagent, be dissolved in manganese element or hydroxyl, carbonate or bicarbonate radical in substitutional element and the precipitation reagent in the solvent generation sediment that reacts.
After obtaining sediment, with said drying precipitate, preferably dry 8h in 80 ℃ of vacuum drying ovens carries out roasting with dried sediment, obtains the positive electrode presoma.The present invention preferably carries out roasting with said sediment in tube furnace, the flow velocity of oxygen is preferably 1mL/min～5mL/min during roasting, more preferably 2mL/min～4mL/min.The temperature of said roasting is preferably 300 ℃～800 ℃, more preferably 400 ℃～600 ℃; The time of said roasting is preferably 1h～10h, more preferably 2h～6h.
After the roasting, obtain containing the compound of manganese, substitutional element and oxygen, with obtaining the positive electrode presoma after said compound cooling, the grinding.Different according to the raw material of selecting for use, contain manganese, oxygen, substitutional element or halogen, N, P, S etc. in the said positive electrode presoma.
After obtaining the positive electrode presoma, be the feedstock production anode material for lithium-ion batteries with this positive electrode presoma.At first said positive electrode presoma, MnS and lithium-containing compound are mixed, carry out then obtaining positive electrode after roasting, the annealing.
In the present invention, said MnS is the crystal face dressing agent, promptly modifies the crystal shape of the positive electrode that obtains, type of obtaining sphaerocrystal.The mol ratio of elemental lithium is preferably (0.001～0.1) in said MnS and the said lithium-containing compound: (0.8～1.2), more preferably (0.005～0.08): (0.9～1.1) most preferably is (0.01～0.05): (0.95～1.05).
In the present invention, said lithium-containing compound is the compound that contains elemental lithium, is preferably in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride and the lithium fluoride one or more, more preferably lithium hydroxide or lithium carbonate.The ratio of the total mole number of manganese element and substitutional element is preferably (0.8～1.2) in the molal quantity of said lithium-containing compound and the said positive electrode: 2, more preferably (0.9～1.1): 2, most preferably be (0.95～1.05): 2.
The present invention preferably with said positive electrode presoma, MnS and lithium-containing compound in batch mixer, add the batch mixing ball and mix, the weight of said batch mixing ball is preferably positive electrode presoma, MnS and lithium-containing compound total weight 2 times.
Said positive electrode presoma, MnS and lithium-containing compound are mixed the back in resistance furnace, carry out roasting, the temperature of said roasting is preferably 750 ℃～1200 ℃, more preferably 800 ℃～1100 ℃, most preferably is 900 ℃～1000 ℃; The time of said roasting is preferably 1h～48h, and more preferably 5h～30h most preferably is 8h～16h.Sintering temperature has considerable influence to the formation and the performance thereof of class sphaerocrystal; The positive electrode crystal structure that obtains under the condition of high temperature is comparatively regular; Sintering temperature is crossed when hanging down, and type sphaerocrystal content is low in the crystal of formation, and the high temperature cyclic performance of the material that obtains is bad.
After roasting finishes, the sintered body that obtains is cooled to room temperature, grinds to form pressed powder, then the pressed powder that obtains is annealed, be about to said pressed powder and be warming up to annealing temperature, obtain positive electrode after the cooling of insulation a period of time.
The present invention preferably anneals said pressed powder in resistance furnace, said annealing temperature is preferably 400 ℃～800 ℃, more preferably 500 ℃～700 ℃, most preferably is 550 ℃～650 ℃; Said annealing time is preferably 1h～12h, and more preferably 2h～6h most preferably is 3h～5h.The positive electrode that annealing in process obtains has better type of spherical morphology, has better filling capacity and high temperature cyclic performance.
After obtaining anode material for lithium-ion batteries, said positive electrode is carried out X-ray diffraction analysis, the result proves that it has the positive spinel of standard (FD-3M) cubic structure, and the free from admixture phase, explains that it can be used as anode material for lithium-ion batteries.
After obtaining anode material for lithium-ion batteries; It is carried out electron microscopic observation, and the result shows that the anode material for lithium-ion batteries that adopts method provided by the invention to prepare is a type sphaerocrystal; It does not have clear and definite corner angle, and the angle between crystal plane and the phase vicinal face is the obtuse angle.Because the dissolving of manganese in electrolyte mainly occurs in the big place of particle curvature, promptly occurs in rib and sharp-pointed summit, because the positive electrode that the present invention prepares does not have rib and sharp-pointed summit basically, therefore, the dissolving of manganese in electrolyte reduces greatly.
In the positive electrode that method provided by the invention prepares, the content of type sphaerocrystal is more than 50%, and is most of more than 90%.In the present invention, type spherical comprises that the superficial growth total or primary particle of the form, the crystal plane that intersect to form between the primary particle goes out between form or the primary particle of the form of other primary particles, primary particle segmental defect the form through the complicated shared formation of crystal plane etc.
The positive electrode that the present invention is prepared places electrolyte, in 60 ℃ of baking ovens, places the meltage of measuring its manganese after 7 days, and experiment shows, the positive electrode of the present invention's preparation under hot conditions in electrolyte the meltage of manganese lower.
The tap density of the positive electrode that mensuration the present invention prepares; And the positive electrode that the present invention is prepared and acetylene black, Kynoar and N-first class pyrrolidones are mixed with and obtain positive plate; And the compacted density of measurement positive plate; The result shows that the positive electrode of the present invention's preparation has the good filling property ability.
The present invention also provides a kind of lithium ion battery; Comprise positive pole, negative pole and place the electrolyte between said positive pole and the negative pole that said positive pole comprises described positive electrode of technique scheme or the positive electrode for preparing through the described method of technique scheme.
In said lithium ion battery, said positive pole comprises the described positive electrode of technique scheme or through the positive electrode that the described method of technique scheme prepares, also comprises conventional materials such as acetylene black, Kynoar.Said positive pole is preferably according to following method preparation:
Positive electrode, acetylene black, Kynoar and solvent that the described positive electrode of technique scheme is perhaps prepared through the described method of technique scheme obtain slurry;
Said slurry is coated in aluminium foil surface, obtains positive pole after compressing.
The present invention does not have particular restriction to the negative pole of said lithium ion battery, can be lithium, silicon or lithium alloy etc., can be the carbon element compounds that lithium ion is emitted in reversible absorptions such as graphite yet.
The present invention does not have particular restriction to the electrolyte of said lithium ion battery, can be liquid electrolyte, can be preferably liquid electrolyte for organic solid electrolyte based or inorganic solid electrolyte yet; When said electrolyte was liquid electrolyte, said electrolyte can be LiClO
4, LiPF
6, LiBF
4, at least a in the lithium salts such as trifluoromethayl sulfonic acid lithium, be preferably LiPF
6Solvent can be carbonic esters such as propylene carbonate, carbonic acid dihexyl; Also can be ether compounds such as sulfolane such as sulfolane, dimethyl sulfoxide (DMSO) or dimethoxy-ethane, being preferably volume ratio is 1: 1 the ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC).
Said positive pole, electrolyte and negative pole are assembled according to method well known in the art, can be obtained lithium ion battery.
After obtaining lithium ion battery, adopt the high temperature test appearance that it is carried out the high temperature cyclic performance test, the result surface, lithium ion battery provided by the invention has the good high-temperature cycle performance under 60 ℃ of temperature.
The present invention at first will contain manganese compound or contain manganese compound and displacer and solvent, obtain containing the manganese sediment or will contain manganese and the sediment of substitutional element after adding precipitation reagent then, with obtaining the positive electrode presoma after the said sediment roasting; With obtaining anode material for lithium-ion batteries after said positive electrode presoma, MnS and lithium-containing compound mixing, roasting, the 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 as lithium ion cell positive.The primary particle of the lithium manganese oxygen positive electrode that method provided by the invention prepares is a type sphaerocrystal; Its crystal plane is continuous through the curved surface that does not have clear and definite rib between the vicinal face with mutually; Crystal plane is the obtuse angle with the angle between the vicinal face mutually, and not only filling rate is higher for a type spherical structure, and makes said lithium manganese oxygen positive electrode have lower specific area; Manganese element at high temperature is difficult for dissolving, thereby has improved its high temperature cyclic performance and filling capacity.
In order to further specify the present invention, anode material for lithium-ion batteries provided by the invention, its preparation method and lithium ion battery are described in detail below in conjunction with embodiment.
According to the raw material shown in the table 1, consumption and condition, prepare lithium manganese oxygen material presoma according to following steps:
In the solution that contains manganese compound, add displacer, slowly drip precipitation reagent under the stirring condition, the pH value of regulating the mixed solution that obtains obtains mixed sediment after the filtration; At vacuum, 80 ℃ of following dry 8h, is the tubular type kiln roasting of 2mL/min with dried mixed sediment at oxygen gas flow rate with said mixed sediment, obtains the presoma of lithium manganese oxygen material.
The prescription and the condition of table 1 embodiment of the invention 1～10 preparation lithium manganese oxygen material presoma
According to the raw material shown in the table 2, consumption and condition, prepare lithium manganese oxygen material according to following steps:
Presoma, lithium-containing compound and the crystal face dressing agent MnS of said lithium manganese oxygen are put into batch mixer; Adding weight is 2 times batch mixing ball mixing of lithium manganese oxygen presoma, lithium salts and crystal face dressing agent total weight; With the mixed material roasting that obtains; Be cooled to room temperature, anneal after grinding, sieving, obtain lithium manganese oxygen material after being cooled to room temperature.
The prescription and the condition of table 2 embodiment of the invention 1～10 preparation lithium manganese oxygen material
The polycrystalline diffractometer that uses German Brooker company carries out X-ray diffraction analysis to the lithium manganese oxygen material of each embodiment preparation; With CuK α line is light source, and the angle of diffraction 2 θ are from 10 ° to 90 °, and the result is referring to Fig. 1; The X ray diffracting spectrum of the lithium manganese oxygen material that Fig. 1 provides for the embodiment of the invention 1; Can know that by Fig. 1 the lithium manganese oxygen material that the embodiment of the invention 1 prepares has positive spinel (FD-3M) cubic structure of standard, and the 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 the free from admixture phase.
Said lithium manganese oxygen material is carried out electron-microscope scanning; The result is referring to 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 invention 1, and the lithium manganese oxygen material that Fig. 3 provides for the embodiment of the invention 2 amplifies 20000 times stereoscan photograph; The lithium manganese oxygen material that Fig. 4 provides for the embodiment of the invention 2 amplifies 40000 times stereoscan photograph; Can know that by Fig. 2, Fig. 3 and Fig. 4 the lithium manganese oxygen material that the present invention prepares does not have clear and definite corner angle for a type sphaerocrystal structure; Crystal plane is the obtuse angle with the angle between the vicinal face mutually, and angle trends towards 0.
Said lithium manganese oxygen material is carried out performance test, and the result is referring to table 3, and table 3 is the performance parameter of the lithium manganese oxygen material of the embodiment of the invention and comparative example preparation.
The LiPF of 1mol/L packs in the 100mL volumetric flask
6Ethylene carbonate (EC) and dimethyl carbonate (DMC) solution, wherein, the volume ratio of EC and DMC is 1: 1; The lithium manganese oxygen material that adds each embodiment preparation of 2g then; Said volumetric flask sealing back was placed 7 days in 60 ℃ of baking ovens, remove lithium manganese oxygen material, collect solution with centrifuge; Use the Optima2100 type inductively coupled plasma emission spectrometer of Perkin-Elmer company to test the manganese content in the said solution, the result is referring to table 4, and table 4 is the manganese dissolving test experiments result that the embodiment of the invention and comparative example provide.
Lithium manganese oxygen material, 1g acetylene black, 1g Kynoar and the 30gN-methyl pyrrolidone of each embodiment preparation of 8g are mixed the formation slurry at normal temperatures and pressures, evenly be coated in aluminium foil surface and make pole piece; Said pole piece is compressed after the oven dry down at 80 ℃, obtain positive plate; Use roll squeezer that said positive plate is carried out roll-in; With micrometer caliper the thickness of positive plate is measured; Write down before the positive plate roll-in respectively and the thickness after the roll-in; Calculate compacted density, the result is referring to table 5, the filling capacity test result of the lithium manganese oxygen material that table 5 provides for the embodiment of the 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; The batch mixing ball that adds 2 times of weight mixes; With the resistance kiln roasting 20h of the mixed material that obtains at 950 ℃; Be cooled to room temperature, the continued of grinding, sieve is at 550 ℃ resistance kiln roasting 10h, obtains lithium manganese oxygen material after being cooled to room temperature, said lithium manganese oxygen material has following atomic ratio: Li
1.05Al
0.1Mn
1.85O
4
Said lithium manganese oxygen material is carried out electron-microscope scanning; The result is referring to Fig. 5, and the stereoscan photograph of the lithium manganese oxygen material that Fig. 5 provides for comparative example 1 of the present invention can be known by Fig. 5; The lithium manganese oxygen material that comparative example 1 prepares is octahedra shape, has sharp-pointed rib and summit.
Said lithium manganese oxygen material is carried out performance test, and the result is referring to table 3, and table 3 is the performance parameter of the lithium manganese oxygen material of the embodiment of the invention and comparative example preparation.
The performance parameter of the lithium manganese oxygen material of table 3 embodiment of the invention and comparative example preparation
Can know that by table 3 the lithium manganese oxygen material that the embodiment of the invention provides has higher tap density, lower specific area and less primary particle average grain diameter.
The LiPF of 1mol/L packs in the 100mL volumetric flask
6Ethylene carbonate (EC) and dimethyl carbonate (DMC) solution, wherein, the volume ratio of EC and DMC is 1: 1; Add the said lithium manganese of 2g oxygen material then; Said volumetric flask sealing back was placed 7 days in 60 ℃ of baking ovens, remove lithium manganese oxygen material, collect solution with centrifuge; Use the Optima2100 type inductively coupled plasma emission spectrometer of Perkin-Elmer company to test manganese 4 content in the said solution, the result is referring to table 4, and table 4 is the manganese 4 dissolving test experiments results that the embodiment of the invention and comparative example provide.
The manganese 4 dissolving test experiments results that table 4 embodiment of the invention and comparative example provide
Can know that by table 4 dissolving of manganese is less than the lithium manganese oxygen material of octahedra shape in the spherical lithium manganese oxygen material of class of embodiment of the invention preparation.
The said lithium manganese of 8g oxygen material, 1g acetylene black, 1g Kynoar and 30gN-methyl pyrrolidone are mixed the formation slurry at normal temperatures and pressures, evenly be coated in aluminium foil surface and make pole piece; Said pole piece is compressed after the oven dry down at 80 ℃, obtain positive plate; Use roll squeezer that said positive plate is carried out roll-in; With micrometer caliper the thickness of positive plate is measured; Write down before the positive plate roll-in respectively and the thickness after the roll-in; Calculate compacted density, the result is referring to table 5, the filling capacity test result of the lithium manganese oxygen material that table 5 provides for the embodiment of the invention and comparative example.
The filling capacity test result of the lithium manganese oxygen material that table 5 embodiment of the invention and comparative example provide
Can know that by table 5 filling capacity of the spherical lithium manganese oxygen material of class of embodiment of the invention preparation is superior to the octahedra shape lithium manganese oxygen material of comparative example 1 preparation.
Lithium manganese oxygen material, 1g acetylene black, 1g Kynoar and the 30gN-methyl pyrrolidone of 8g embodiment 1 preparation are mixed the formation slurry at normal temperatures and pressures, evenly be coated in aluminium foil surface and make pole piece; Said pole piece is compressed after the oven dry down at 80 ℃, and being cut into area is 1.32cm
2Thin rounded flakes as positive pole, be negative pole with the pour lithium slice, 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 being full of the glove box of argon gas, is assembled into lithium ion battery.
Use the high temperature test appearance that said lithium ion battery is carried out the cycle performance test, probe temperature is 60 ℃, and charging and discharging currents is 0.4mA/cm
2Charging grafting voltage is 4.35V, and discharge cut-off voltage is 3.0V, and the result is referring to Fig. 6; The high temperature circulation curve of the lithium ion battery that Fig. 6 provides for the embodiment of the invention and comparative example; Wherein, the high temperature circulation curve of the lithium ion battery that curve 1 provides for the embodiment of the 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 of 1 preparation of 8g comparative example are mixed the formation slurry at normal temperatures and pressures, evenly be coated in aluminium foil surface and make pole piece; Said pole piece is compressed after the oven dry down at 80 ℃, and being cut into area is 1.32cm
2Thin rounded flakes as positive pole, be negative pole with the pour lithium slice, 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 being full of the glove box of argon gas, is assembled into lithium ion battery.
Use the high temperature test appearance that said lithium ion battery is carried out the cycle performance test, probe temperature is 60 ℃, and charging and discharging currents is 0.4mA/cm
2Charging is 4.3V by voltage, and discharge cut-off voltage is 3.0V, and the result is referring to Fig. 6; The high temperature circulation curve of the lithium ion battery that Fig. 6 provides for the embodiment of the invention and comparative example; Wherein, the high temperature circulation curve of the lithium ion battery that curve 1 provides for the embodiment of the invention 11, the high temperature circulation curve of the lithium ion battery that curve 2 provides for comparative example 2 of the present invention.Can know that by Fig. 6 the high temperature cyclic performance of the lithium ion battery that the embodiment of the invention provides is superior to the high temperature cyclic performance of the lithium ion battery that comparative example 2 provides.
Can know by the foregoing description and comparative example, the lithium manganese oxygen material that method provided by the invention can type of preparing spherical structure, it has good high-temperature cycle performance and filling capacity.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (13)
1. anode material for lithium-ion batteries has the atomic ratio shown in the formula (I) and forms:
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 among 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 the Si;
Z is one or more among OH, halogen, N, P, S and the O;
Primary particle type of the having spherical morphology of said positive electrode, its (111) face is connected through the curved surface that does not have clear and definite rib with adjacent equivalent crystal.
2. anode material for lithium-ion batteries according to claim 1 is characterized in that, the particle diameter of the primary particle of said positive electrode is 1 μ m～20 μ m.
3. the preparation method of an anode material for lithium-ion batteries may further comprise the steps:
A) will contain manganese compound and solvent, obtain containing manganese compound solution;
B) containing in the manganese compound solution of obtaining add precipitation reagent to said step a), obtain sediment, said precipitation reagent is alkali-metal hydroxide solution, alkali-metal carbonate solution or alkali-metal bicarbonate solution;
C) the sediment roasting that said step b) is obtained obtains the positive electrode presoma;
D) the positive electrode presoma that said step c) is obtained, MnS and lithium-containing compound mix the back roasting, obtain pressed powder after the grinding;
E) pressed powder that said step d) is obtained carries out annealing in process, obtains anode material for lithium-ion batteries.
4. preparation method according to claim 3 is characterized in that, said step a) specifically comprises:
To contain manganese compound mixes in solvent with displacer; Obtain containing manganese compound solution, said displacer is to contain the Li compound, contain the Na compound, contain the K compound, contain the Ca compound, contain the Mg compound, contain the Al compound, contain the Ti compound, contain the Sc compound, contain the Ge compound, contain the V compound, contain the Cr compound, contain the Zr compound, contain the Co compound, contain the Ni compound, contain the Zn compound, contain the Cu compound, contain the La compound, contain the Ce compound, contain the Mn compound, contain the Hf compound, contain the Nb compound, contain the Ta compound, contain the Mo compound, contain the W compound, contain the Ru compound, contain the Ag compound, contain the Sn compound, contain the Pb compound and contain in the Si compound one or more.
5. preparation method according to claim 4 is characterized in that, the said manganese compound that contains is in manganese sulfate, manganese carbonate, manganese nitrate, manganese chloride and the manganese oxalate one or more.
6. preparation method according to claim 4 is characterized in that, said solvent is water, methyl alcohol, ethanol or acetone.
7. preparation method according to claim 3 is characterized in that, said step b) is specially:
Containing in the manganese compound solution of obtaining add precipitation reagent to said step a), regulate pH value to 6～13, obtain sediment.
8. preparation method according to claim 3 is characterized in that, in the said step d), said lithium-containing compound is one or more in lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium chloride and the lithium fluoride.
9. preparation method according to claim 3 is characterized in that, in the said step d), the mol ratio of elemental lithium is (0.001～0.1) in said MnS and the said lithium-containing compound: (0.8～1.2).
10. according to any described preparation method of claim 3～9, it is characterized in that in the said step c), the temperature of said roasting is 300 ℃～800 ℃, the time of said roasting is 1h～10h.
11., it is characterized in that in the said step d), the temperature of said roasting is 750 ℃～1200 ℃ according to any described preparation method of claim 3～9, the time of said roasting is 1h～48h.
12., it is characterized in that in the said step e), the temperature of said annealing is 400 ℃～800 ℃ according to any described preparation method of claim 3～9, the time of said annealing is 1h～12h.
13. lithium ion battery; Comprise positive pole, negative pole and place the electrolyte between said positive pole and the negative pole; It is characterized in that said positive pole comprises claim 1 or 2 described positive electrodes or through any positive electrode that described method prepares of claim 3～12.
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| 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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