CN109873131A - Positive battery material and preparation method thereof and anode and all-solid-state battery - Google Patents

Positive battery material and preparation method thereof and anode and all-solid-state battery Download PDF

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CN109873131A
CN109873131A CN201711262619.XA CN201711262619A CN109873131A CN 109873131 A CN109873131 A CN 109873131A CN 201711262619 A CN201711262619 A CN 201711262619A CN 109873131 A CN109873131 A CN 109873131A
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solution
lamella
lithium
reaction
composite oxide
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CN109873131B (en
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韩晓燕
焦晓朋
李世彩
郭姿珠
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BYD Co Ltd
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BYD Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention relates to all-solid-state battery fields, and in particular to positive battery material and preparation method thereof and anode and all-solid-state battery.Wherein, the positive electrode material is MnO2Conducting base lamella and lithium-contained composite oxide lamella, the MnO2Conducting base lamella and the lithium-contained composite oxide lamella are alternately stacked, and the composition of the lithium-contained composite oxide lamella includes Li1+xL1-y- zMyNzO2And/or LiNi0.5‑x1Mn1.5‑y1Ax1+y1O4.Positive battery material of the invention conductivity itself can satisfy all-solid-state battery charge-discharge power demand, not need additionally to add conductive agent.

Description

Positive battery material and preparation method thereof and anode and all-solid-state battery
Technical field
The present invention relates to all-solid-state battery fields, and in particular to positive battery material and preparation method thereof and battery are just Pole and all-solid-state battery.
Background technique
Lithium ion battery currently on the market is mostly using liquid electrolyte as conductive materials, but in use, liquid Electrolyte is volatile, inflammable and explosive, leads to many safety problems；And it easily grows Li dendrite, limits lithium metal as negative The application of pole in the battery.Therefore, it has been proposed that substituting liquid electrolyte with solid polymer electrolyte (SPE).
Lithium ion battery has been widely used for portable electronics, electric car, extensive energy storage and other power supply devices In.With the extensive use of lithium ion battery, the problem of secure context, also has been to be concerned by more and more people and payes attention to.Quan Gu State lithium ion battery avoids liquid electrolyte leakage and Organic Electricity in liquid lithium ionic cell because using solid electrolyte The inflammable problem of liquid is solved, becomes a kind of effective way for solving lithium ion battery safety problem, becomes current lithium ion battery and grind Heat generating spot.
The preparation method of all-solid lithium-ion battery has magnetron sputtering method, cold-press method, pulsed laser deposition, the tape casting etc..Its Middle the tape casting has many advantages, such as that simple production process, production cost are low and suitable for mass production.It is complete solid using casting technique preparation State electrodes of lithium-ion batteries can substantially reduce all-solid-state battery production cost and pole piece thickness.It is prepared using the tape casting inorganic All-solid lithium-ion battery, i.e., by active material and binder, dispersing agent etc. is evenly dispersed in a solvent, by scattered slurry Curtain coating, then by positive and negative anodes cast sheet and the lamination hot pressing of solid electrolyte cast sheet, cuts into particular size on basis material Shape, carry out high temperature remove glue integrated treatment, can be obtained required all-solid-state battery.
The active material that CN201310726380.2 discloses combination electrode is uniformly strapped in by carbon nanotube interconnection In the three-dimensional porous network of formation, in the hole that three-dimensional network is formed and surface of active material is filled or cladding solid electrolytic material Material forms combination electrode；Three-dimensional porous network material (is used for transmission electronics), and active material is used for transmission ion (active material Selected from anode material for lithium-ion batteries or negative electrode material).The material of the patent disclosure is preparing all solid lithium for casting technique When ion battery anode, CO is generated except carbon nanotube can aoxidize in glue process, under oxygen atmosphere in high temperature2, lose electric conductivity. And high temperature removes glue under inert atmosphere, then can make LiCoO2, NCA, NCM, LiNi0.5Mn1.5O4The transition of high-valence state in equal positive electrodes Metal is reduced to lower valency by carbon, loses activity so as to cause electrode active material.
Patent CN201410623686.X roasted after then mixing manganese dioxide with the positive electrode of conductive sub- diversion and At；Wherein MnO2For active material.The working principle of material is to utilize MnO2Oxidisability, i.e. every mole of MnO2It can receive Two moles of electronics becomes MnO and Li2O.And traditional positive electrode such as LiFePO4, LiCoO2Deng then serve as electronics and lithium from Sub- conductor.The voltage platform of the material is 2.5~3.0V.
In addition, the tape casting prepares all-solid-state battery, the positive plate being cast out is required to remove glue except glue process by high temperature On the one hand process removes the binder added in casting slurry, on the other hand pass through high temperature sintering, cast sheet can be made more to cause It is close.To the anode material for lithium-ion batteries with certain oxidisability for example, LiCoO2, NCA, NCM, LiNi0.5Mn1.5O4Deng the height Temperature carries out in air atmosphere except adhesive process needs, in case transition metal is in an inert atmosphere by binder high temperature point in positive electrode The carbon reduction that solution generates.The high temperature carried out under air atmosphere removes glue process, then determines the positive cast sheet of this method preparation not It can be using the conductive agent of carbon class and metal simple-substance class, because above two conductive agent can occur under air atmosphere and high temperature Oxidation reaction loses conductive subfunction.
For these reasons when the tape casting prepares lithium ion cell positive cast sheet, conductive agent routinely cannot make With.Therefore, it is necessary to research and develop a kind of positive battery material not needed using conductive agent, and it can satisfy all-solid-state battery charge and discharge Electricity demanding is of great significance.
Summary of the invention
The purpose of the invention is to overcome the above problem of the existing technology, provide a kind of positive battery material and Preparation method and anode and all-solid-state battery.
To achieve the goals above, first aspect present invention provides a kind of positive battery material, wherein the positive electricity Pole material includes MnO2Conducting base lamella and lithium-contained composite oxide lamella, the MnO2Conducting base lamella and it is described contain lithium Composite oxides lamella is alternately stacked, and the composition of the lithium-contained composite oxide lamella includes Li1+xL1-y-zMyNzO2And/or LiNi0.5-x1Mn1.5-y1Ax1+y1O4；
Wherein, at least one of L, M, N Li, Co, Mn, Ni, Al, Mg, Ga, Ti, Cr, Cu, Zn and Mo, -0.1≤x ≤ 0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0；
Wherein, -0.1≤x1≤ 0.5,0≤y1In≤1.5, A Li, Co, Al, Mg, Ca, Ti, Mo, Cr, Cu and Zn extremely Few one kind.
Second aspect of the present invention provides a kind of preparation method of positive battery material, wherein this method includes following Step:
(1) in the presence of 50-160 DEG C, mixed solvent, the first reaction of manganese carbonate raw material progress will be prepared and obtained containing manganese carbonate The solution E of lamella；In 180-250 DEG C, solution E, it is anti-that the solution of the presoma containing lithium-contained composite oxide is carried out second It should obtain the solution F containing lithium-contained composite oxide lamella；Again in solution F, the first reaction, the second reaction are repeated；It is suitable according to this Sequence makes manganese carbonate lamella successively be superimposed growth with lithium-contained composite oxide lamella；Manganese carbonate is prepared in first reaction every time The amount of raw material is identical or different；The amount of the solution of the presoma containing lithium-contained composite oxide is identical in second reaction every time Or it is different；
(2) product of step (1) is subjected to high-temperature heat treatment；
The mixed solvent include water and containing hydroxyl and can azeotrope with water organic solvent.
Third aspect present invention provides a kind of preparation method of positive battery material, wherein this method comprises:
In the presence of 190-210 DEG C, surfactant, the first reaction is occurred into for the raw material for preparing manganese dioxide and is contained MnO2The solution G of lamella, in solution G, the solution of the presoma containing lithium-contained composite oxide carries out the second reaction and is contained There is the Solution H of lithium-contained composite oxide lamella；Again in Solution H, the first reaction, the second reaction are repeated；Sequence according to this, makes dioxy Change manganese lamella and is successively superimposed growth with lithium-contained composite oxide lamella；The raw material of manganese dioxide is prepared in first reaction every time Amount it is identical or different；The amount of the solution of the presoma containing lithium-contained composite oxide is identical or not in second reaction every time Together；
Wherein, the raw material for preparing manganese dioxide includes soluble manganese salting liquid E and soluble manganese salting liquid F, wherein The soluble manganese salting liquid E be include Mn+n, and the soluble manganese salting liquid E of n > 4；The soluble manganese salting liquid F is packet Include Mn+m, and the soluble manganese salting liquid F of m≤3.
Fourth aspect present invention provides a kind of anode, wherein the anode contains positive electricity described above Positive electrode material made from pole material or method described above.
Fifth aspect present invention provides a kind of all-solid-state battery, wherein the all-solid-state battery includes: anode, electrolyte Layer and cathode, the anode just extremely described above.
The present invention uses MnO2As conducting base, in sheet MnO2Lithium-contained composite oxide lamella is stacked on conducting base, MnO2Lamella is successively alternately stacked with lithium-contained composite oxide lamella, is forming positive electrode material made of stacked in multi-layers (compound just Pole material).The positive electrode is after high-temperature process, because positive electrochemical oxidation can be undergone to restore MnO in anode2, because This does not influence its electric conductivity.In addition, MnO2Electrochemistry or change does not occur in charge and discharge process as electronic conduction skeleton Reaction is learned, remains MnO2Structure is constant.MnO2Electronic conductivity can reach the 1.0S/cm order of magnitude, and traditional lithium ion Cell positive material, such as LiCoO2Then there was only 10-4Therefore S/cm cannot be born simultaneously in carbons and metal class conductive agent When high temperature and oxygen atmosphere condition, the positive electrode material proposed by the present invention made of stacked in multi-layers is conductive without adding Agent, and can satisfy the requirement of inorganic full-solid lithium ion battery.
Detailed description of the invention
Fig. 1 is the SEM electromicroscopic photograph of positive electrode material P1 prepared by the embodiment of the present invention 1；
Fig. 2 is SEM electromicroscopic photograph before positive electrode material P1 prepared by the embodiment of the present invention 1 charges；
Fig. 3 is SEM electromicroscopic photograph after positive electrode material P1 electric discharge prepared by the embodiment of the present invention 1；
Fig. 4 is positive electrode material P1 prepared by the embodiment of the present invention 1 and cobalt acid lithium sintered sheets C1 in 0.5C charge and discharge Curve comparison figure.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of positive electrode materials, wherein the positive electrode material includes MnO2Conductive base Body lamella and lithium-contained composite oxide lamella, the MnO2Conducting base lamella and the lithium-contained composite oxide lamella replace heap Folded, the composition of the lithium-contained composite oxide lamella includes Li1+xL1-y-zMyNzO2And/or LiNi0.5-x1Mn1.5-y1Ax1+y1O4；
Wherein, at least one of L, M, N Li, Co, Mn, Ni, Al, Mg, Ga, Ti, Cr, Cu, Zn and Mo, -0.1≤x ≤ 0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0；
Wherein, -0.1≤x1≤ 0.5,0≤y1In≤1.5, A Li, Co, Al, Mg, Ca, Ti, Mo, Cr, Cu and Zn extremely Few one kind.
According to the present invention, the MnO2Conducting base lamella refers to the MnO on same plane2The lamella of substance；Equally, The lithium-contained composite oxide lamella again refers to the lithium-contained composite oxide lamella on same plane.
In the case of, according to the invention it is preferred to, the positive electrode material has one or more repetitive units, wherein each A repetitive unit is with MnO2Conducting base lamella is as support construction, and in the MnO2The upper surface of conducting base lamella The lithium-contained composite oxide lamella and the MnO are stacked with following2Conducting base lamella is less than the composite oxygen containing lithium Compound lamella.
According to the invention, it is further possible to include another situation, that is, the positive electrode material has one or more repetitions single Member, wherein each repetitive unit is using lithium-contained composite oxide lamella as support construction, and in the combined oxidation containing lithium The upper surface of object lamella is stacked with the MnO with following2Conducting base lamella and the lithium-contained composite oxide lamella are less than institute State MnO2Conducting base lamella.
Preferably, the length of the lithium-contained composite oxide lamella is 100nm-2 μm, each lithium-contained composite oxide Lamella with a thickness of 10nm-250nm, each MnO2Conducting base lamella with a thickness of 10nm-200nm；It is highly preferred that institute State lithium-contained composite oxide lamella length be 200nm-1 μm, each lithium-contained composite oxide lamella with a thickness of 10nm- 200nm, each MnO2Conducting base lamella with a thickness of 10nm-160nm；It is further preferred that the composite oxygen containing lithium The length of compound lamella be 300-600nm, each lithium-contained composite oxide lamella with a thickness of 10nm-150nm, Mei Gesuo State MnO2Conducting base lamella with a thickness of 10nm-100nm.In the case of in the present invention, it is preferred to, the lithium-contained composite oxide The length of lamella refers to being formed by the distance of most strong point in lamellar structure at it, also, stacks between lamella and lamella There is MnO2Conducting base, the MnO2Conducting base is also laminated structure, and the MnO of sheet2Conducting base is between composite oxygen containing lithium Compound is formed by between lamella, that is to say, that the MnO of the sheet2The length of conducting base is less than the composite oxygen containing lithium The length of compound lamella.
According to the present invention, using the MnO2Layer is used as conducting base, by sheet MnO2Conducting base is stacked on composite oxygen containing lithium On compound lamella, MnO2Conducting base lamella and lithium-contained composite oxide lamella are alternately stacked, and are formed made of stacked in multi-layers just Electrode material (composite positive electrode material).When the positive electricity electrode material have above-mentioned stacked in multi-layers structure, and it is described layer by layer When stacked structure has above-mentioned property, when by high-temperature process, lower than 600 DEG C components will not change the positive electrode, Even if MnO after being more than 600 DEG C except glue temperature2Conducting matrix grain meeting decomposed is Mn2O3, part Mn2O3Then in cathode voltage MnO is all oxidized to when higher than 4.0V2, its electric conductivity is not influenced.In addition, MnO2As electronic conduction skeleton in charge and discharge Electrochemistry or chemical reaction does not occur in the process, remains MnO2Structure is constant, proposed by the present invention to use stacked in multi-layers Made of positive electrode material, without adding conductive agent, and can satisfy the requirement of inorganic full-solid lithium ion battery.
According to the present invention, the partial size D50 of the positive electrode material can be 50nm-3 μm；It is further preferred that it is described just The partial size D50 of electrode material is 50nm-1 μm.It, can when the partial size of the positive electrode material is within above-mentioned limited range Guarantee the curtain coating effect of casting technique, realizes cast sheet densification.
According to the present invention, the lithium-contained composite oxide lamella and MnO2The consumption proportion of conducting base can be in wider model Enclose interior variation, it is preferable that on the basis of the total weight of the positive battery material, the MnO2The content of conducting base is 5- 40 weight %, preferably 10-25 weight %, more preferably 10-15 weight %.
According to the present invention, the specific type of the lithium-contained composite oxide lamella is not limited specifically, is normal Raw material is advised, can be selected according to demand.For example, the composition of the lithium-contained composite oxide lamella includes but is not limited to Li1+ xL1-y-zMyNzO2And/or LiNi0.5-x1Mn1.5-y1Ax1+y1O4；Wherein, L, M, N Li, Co, Mn, Ni, Al, Mg, Ga, Ti, Cr, At least one of Cu, Zn and Mo, -0.1≤x≤0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0；Wherein, -0.1≤x1 ≤ 0.5,0≤y1At least one of≤1.5, A Li, Co, Al, Mg, Ca, Ti, Mo, Cr, Cu and Zn.Under preferable case, institute The group for stating lithium-contained composite oxide lamella becomes cobalt acid lithium (LiCoO2), LiNi1-y2-z2Coy2Mnz2O2(wherein, 0≤y2≤1,0 ≤ z2≤1,0≤y2+z2≤1.0), LiNi0.85Co0.15Al0.05O2And LiNi0.5Mn1.5O4One of or it is a variety of.
Second aspect, the present invention provides a kind of preparation methods of positive electrode material, wherein this method includes following step It is rapid:
(1) in the presence of 50-160 DEG C, mixed solvent, the first reaction of manganese carbonate raw material progress will be prepared and obtained containing manganese carbonate The solution E of lamella；In 180-250 DEG C, solution E, it is anti-that the solution of the presoma containing lithium-contained composite oxide is carried out second It should obtain the solution F containing lithium-contained composite oxide lamella；Again in solution F, the first reaction, the second reaction are repeated；It is suitable according to this Sequence makes manganese carbonate lamella successively be superimposed growth with lithium-contained composite oxide lamella；Manganese carbonate is prepared in first reaction every time The amount of raw material is identical or different；The amount of the solution of the presoma containing lithium-contained composite oxide is identical in second reaction every time Or it is different；
(2) product of step (1) is subjected to high-temperature heat treatment；
The mixed solvent include water and containing hydroxyl and can azeotrope with water organic solvent.
Preparation method according to the present invention, the solution F containing lithium-contained composite oxide lamella are to drip LiOH solution It is added in soluble salt solutions, is then obtained by mixing obtained mixture and oxidant, wherein the soluble-salt The range of solution can select in wider range, for example, the soluble salt solutions can for containing cobalt salt, nickel salt, One of manganese salt, aluminium salt, magnesium salts, gallium salt, titanium salt, chromic salts, mantoquita, zinc salt and molybdenum salt or a variety of aqueous solutions；Preferably, institute Stating soluble salt solutions is containing Co (NO3)2、NiCl2、Ni(NO3)2、MnCl2With Al (NO3)3One of or it is a variety of water-soluble Liquid；In addition, the oxidant can be H2O2And/or sodium hypochlorite, preferably H2O2。
Preparation method according to the present invention, under preferable case, preparing manganese carbonate raw material includes that manganese salt solution A and carbonate are molten Liquid B；In more preferable situation, the manganese salt solution A can be for containing manganese oxalate, manganese acetate, manganese chloride, manganese nitrate, in manganese sulfate One or more aqueous solutions；The carbonate solution B can be the aqueous solution containing ammonium carbonate and/or ammonium hydrogen carbonate, more Under preferable case, the carbonate solution B is the aqueous solution containing ammonium carbonate；It is described containing hydroxyl and can azeotrope with water it is organic Solvent can be to contain at least one of diglycol, ethylene glycol, triethylene glycol and tetraethylene glycol.
Preparation method according to the present invention, wherein described to contain hydroxyl and the energy organic solvent of azeotrope with water and the use of water The volume ratio of amount can be (35-45): 1；Under preferable case, it is described containing hydroxyl and can azeotrope with water organic solvent and water The volume ratio of dosage is 40:1.
In the present invention, when the organic solvent containing hydroxyl and energy azeotrope with water is selected from diglycol, ethylene glycol, three When any one in glycol and tetraethylene glycol, for example, it is to be understood that diglycol, ethylene glycol, triethylene glycol or tetraethylene glycol Volume ratio with the dosage of water can be (35-45): 1；
When the organic solvent containing hydroxyl and energy azeotrope with water is sweet selected from diglycol, ethylene glycol, triethylene glycol and four When any two kinds in alcohol, for example, it is to be understood that the volume of the dosage of the total dosage and water of diglycol and ethylene glycol Than that can be (35-45): 1, alternatively, the volume ratio of the dosage of the total dosage and water of diglycol and triethylene glycol can be (35-45): 1, alternatively, the volume ratio of the dosage of the total dosage and water of diglycol and tetraethylene glycol can be (35-45): 1, Alternatively, the volume ratio of the dosage of the total dosage and water of ethylene glycol and triethylene glycol can be (35-45): 1, alternatively, ethylene glycol and four The volume ratio of the dosage of total dosage and water of glycol can be (35-45): 1, alternatively, the total dosage and water of triethylene glycol and tetraethylene glycol The volume ratio of dosage can be (35-45): 1；
When the organic solvent containing hydroxyl and energy azeotrope with water is sweet selected from diglycol, ethylene glycol, triethylene glycol and four When any three kinds in alcohol, for example, it is to be understood that the use of diglycol, total dosage of ethylene glycol and triethylene glycol and water The volume ratio of amount can be (35-45): 1, alternatively, the dosage of diglycol, total dosage of ethylene glycol and tetraethylene glycol and water Volume ratio can be (35-45): 1, alternatively, the volume ratio of the dosage of ethylene glycol, total dosage of triethylene glycol and tetraethylene glycol and water Can be (35-45): 1, alternatively, the volume ratio of the dosage of diglycol, total dosage of triethylene glycol and tetraethylene glycol and water can Think (35-45): 1；
When the organic solvent containing hydroxyl and energy azeotrope with water is sweet selected from diglycol, ethylene glycol, triethylene glycol and four When the mixture of alcohol, for example, it is to be understood that diglycol, ethylene glycol, total dosage of triethylene glycol and tetraethylene glycol and water The volume ratio of dosage can be (35-45): 1.
In the present invention, diglycol, ethylene glycol, triethylene glycol or tetraethylene glycol are not involved in reaction, only with water energy azeotropic It is to provide reaction platform with hydroxyl, first is that medium temperature, second is that playing the role of controlling the partial size and pattern of material.
Preparation method according to the present invention, wherein be added in first reaction or repetition first reaction Total dosage of the part solution A and the part solution B and the volume ratio of the mixed solvent can be 2:(50-500)；Institute It states the second reaction or repeats the presoma containing lithium-contained composite oxide described in the part being added in second reaction The dosage of solution and the volume ratio of the mixed solvent can be 1:(5-100).
Preferably, solution A, solution B, LiOH solution, soluble salt solutions, oxidant and contain hydroxyl and can azeotrope with water The molar ratio of dosage of solution D can be 1:(1-1.2): (5-40): (2.5-20): (2-15): (30-100), preferably 1: (1-1.05): (10-20): (5-10): (3-10): (50-100).
Preparation method according to the present invention, wherein it is 50-160 DEG C that the condition of first reaction, which includes: temperature, at this In invention, temperature is 50-160 DEG C, refers to that temperature can be the arbitrary value between 50-160 DEG C, for example, temperature can be 50 ℃、51℃、52℃、53℃、54℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C etc., herein It is no longer superfluous to lift, similar below, time 1min-1h；Preferably, temperature is 110-130 DEG C, time 2-50min；Described second The condition of reaction includes: that temperature is 180-250 DEG C, time 1h-2h；Preferably, temperature is 190-210 DEG C, time 70- 150min。
Preparation method according to the present invention, when repeat first reaction and second reaction, that is to say, that carry out third reaction and When the 4th reaction, the reaction condition of the third reaction is identical as the reaction condition of first reaction, the 4th reaction Reaction condition is identical as the reaction condition of second reaction, that is, it is 50-160 that the condition of the third reaction, which includes: temperature, DEG C, the time is 1min-1h hours；It is 180-250 DEG C that the reaction condition of 4th reaction, which includes: temperature, time 30min- 2h。
It is highly preferred that it is 115-125 DEG C that the condition of first reaction, which includes: temperature, time 45min；Described second The condition of reaction includes: that temperature is 195-205 DEG C, time 1.5h；It is 115- that the condition of the third reaction, which includes: temperature, 125 DEG C, time 45min；It is 195-205 DEG C that the condition of 4th reaction, which includes: temperature, time 30min-2h.
That is, the reaction condition for repeating the first reaction is identical as the reaction condition of first reaction, second is repeated The reaction condition of reaction is identical as the reaction condition of second reaction.
Preferably, the rate that the LiOH solution is added dropwise can be 0.5-2 ml/min.
Preferably, repeating the first reaction and the second reaction, be related to manganese salt solution A, carbonate solution B and contain There are the several parts of solution point of the presoma of lithium-contained composite oxide to be reacted, wherein in each section, manganese salt solution A, carbon There is no particular limitation for the specific dosage of the solution of acid salt solution B and the presoma containing lithium-contained composite oxide, as long as full The solution of manganese salt solution A, carbonate solution B and the presoma containing lithium-contained composite oxide are participated in reaction i.e. by foot by different level Can, for example, in the present invention, firstly, a part of solution A and a part of solution B are added in the presence of mixed solvent, so that Added a part of solution A carries out first with a part of solution B and reacts, and then, stops addition solution A and solution B, wait react After the completion, a part of manganese carbonate lamella can be obtained；Then, the solution of the presoma by a part containing lithium-contained composite oxide The second reaction is carried out, to after the reaction was completed, in the upper surface of obtained a part of manganese carbonate lamella and following each can stack one Part lithium-contained composite oxide lamella；Then, then in the presence of mixed solvent, by another part manganese salt solution A and another portion Point carbonate solution B carries out third reaction, can be in obtained a part of lithium-contained composite oxide lamella to after the reaction was completed The upper surface of stack another part manganese carbonate lamella；Again at high temperature, another part is contained to the presoma of lithium-contained composite oxide Solution carry out the 4th reaction and the upper surface of obtained another part manganese carbonate lamella stack another part composite oxygen containing lithium Compound lamella；
The rest may be inferred, can also carry out the 5th reaction and the 6th reaction, that is, again by part manganese salt solution A+ part thereof Solution B carries out the 5th reaction, then the solution of the presoma by part containing lithium-contained composite oxide carries out the 6th reaction, according to need Stop reaction or as needed until by manganese salt solution A, carbonate solution B and containing the presoma of lithium-contained composite oxide Solution amount use up until；In the present invention, pass through the above-mentioned reaction process of strict control, wherein manganese salt solution A, carbonate Ratio between solution B and the solution of the presoma containing lithium-contained composite oxide can need to be adjusted according to experiment, energy Positive electrode material made of stacked in multi-layers is accessed, and the positive electrode of different conducting bases and lithium-contained composite oxide can be obtained Material.
In addition, in the present invention, the reaction condition for having manganese salt solution A and carbonate solution B to participate in is all the same, for example, ginseng It is admitted to the reaction condition for stating the first reaction and third reaction；There is the solution of the presoma containing lithium-contained composite oxide to participate in anti- Answer condition all the same, for example, with reference to the reaction condition of above-mentioned second reaction and the 4th reaction.
Preparation method according to the present invention, in step (2), the condition of the high-temperature heat treatment may include: that temperature is 300-500 DEG C, the time is 5-24 hours；In the present invention, obtained in step (1) successively be superimposed growth manganese carbonate lamella with Lithium-contained composite oxide lamella, the manganese carbonate lamella and lithium-contained composite oxide lamella of the layer-by-layer superposition growth are through step (2) After high-temperature process, manganese carbonate lamella high-temperature oxydation obtains MnO2Lamella, that is, MnO2Conducting base lamella, and then be successively superimposed The MnO of growth2Lamella and lithium-contained composite oxide lamella.
Preparation method according to the present invention, the reaction (hydro-thermal reaction) carries out under stirring conditions, for stirring Equipment is not particularly limited, for example, can be agitating paddle, mixing pump etc.；Stirring rate is also not particularly limited, for example, can Think 50-500 revs/min.
The equipment of preparation method according to the present invention, the reaction (hydro-thermal reaction) is not particularly limited, for example, can be It is carried out in hydrothermal reaction kettle.
Preparation method according to the present invention, wherein the length of the lithium-contained composite oxide lamella is 100nm-2 μm, often A lithium-contained composite oxide lamella with a thickness of 10nm-250nm, each MnO2Conducting base lamella with a thickness of 10nm-200nm；
Preferably, the length of the lithium-contained composite oxide lamella is 200nm-1 μm, each lithium-contained composite oxide Lamellar spacing is 10nm-200nm, each MnO2Conducting base lamella with a thickness of 10nm-160nm；
It is further preferred that the length of the lithium-contained composite oxide lamella is 300-600nm, it is each described compound containing lithium Oxide lamella with a thickness of 10nm-150nm, each MnO2Conducting base lamella with a thickness of 10nm-100nm.
According to a preferred embodiment of the present invention, a kind of preparation method of positive electrode material the following steps are included:
(1) manganese salt solution A is prepared；
(2) carbonate solution B is prepared；
(3) LiOH solution is added drop-wise in soluble salt solutions, obtained mixture is mixed with oxidant then, is obtained To the solution of the presoma containing lithium-contained composite oxide；
(4) mixed solvent of including water and containing hydroxyl and energy azeotrope with water organic solvent is prepared；
(5) at low temperature, in the presence of mixed solvent, a part of solution A and a part of solution B are subjected to the first reaction Obtain a part of manganese carbonate lamella；Again at high temperature, the solution of the presoma by a part containing lithium-contained composite oxide carries out Second reaction simultaneously respectively stacks a part of lithium-contained composite oxide piece with following in the upper surface of obtained a part of manganese carbonate lamella Layer；
Then, then at low temperature, in the presence of mixed solvent, another part solution A and another part solution B are carried out Third reaction simultaneously stacks another part manganese carbonate lamella in the upper surface of obtained a part of lithium-contained composite oxide lamella；Exist again Under high temperature, the solution that another part contains the presoma of lithium-contained composite oxide is subjected to the 4th reaction and obtained another The upper surface of part manganese carbonate lamella stacks another part lithium-contained composite oxide lamella；
Sequence according to this, makes manganese carbonate lamella successively be superimposed growth with lithium-contained composite oxide lamella, stops at any time as needed Only feed and then stop reaction or as needed until by manganese salt solution A, carbonate solution B and containing lithium-contained composite oxide Presoma solution amount use up until；
(6) product of step (5) is subjected to high-temperature heat treatment, obtains the MnO for being successively superimposed growth2Lamella with containing lithium it is compound Oxide lamella.
The third aspect, the present invention provides a kind of preparation methods of positive electrode material, wherein this method includes following step It is rapid:
In the presence of 190-210 DEG C, surfactant, the first reaction is occurred into for the raw material for preparing manganese dioxide and is contained MnO2The solution G of lamella, in solution G, the solution of the presoma containing lithium-contained composite oxide carries out the second reaction and is contained There is the Solution H of lithium-contained composite oxide lamella；Again in Solution H, the first reaction, the second reaction are repeated；Sequence according to this, makes dioxy Change manganese lamella and is successively superimposed growth with lithium-contained composite oxide lamella；The raw material of manganese dioxide is prepared in first reaction every time Amount it is identical or different；The amount of the solution of the presoma containing lithium-contained composite oxide is identical or not in second reaction every time Together；
Wherein, the raw material for preparing manganese dioxide includes soluble manganese salting liquid E and soluble manganese salting liquid F, wherein The soluble manganese salting liquid E be include Mn+n, and the soluble manganese salting liquid E of n > 4；The soluble manganese salting liquid F is packet Include Mn+m, and the soluble manganese salting liquid F of m≤3.
Preparation method according to the present invention, the solution of the presoma containing lithium-contained composite oxide are by LiOH solution It is added drop-wise in soluble salt solutions, is then obtained by mixing obtained mixture and oxidant, wherein the solubility The range of salting liquid can select in wider range, for example, the soluble salt solutions can be to contain cobalt salt, nickel One of salt, manganese salt, aluminium salt, magnesium salts, gallium salt, titanium salt, chromic salts, mantoquita, zinc salt and molybdenum salt or a variety of aqueous solutions；It is preferred that Ground, the soluble salt solutions are to contain Co (NO3)2、NiCl2、Ni(NO3)2、MnCl2With Al (NO3)3One of or it is a variety of Aqueous solution；In addition, the oxidant can be H2O2And/or sodium hypochlorite, preferably H2O2。
Preparation method according to the present invention, under preferable case, the soluble manganese salting liquid F is to contain manganese oxalate, acetic acid One of manganese, manganese chloride, manganese nitrate and manganese sulfate or a variety of aqueous solutions；The soluble manganese salting liquid E is KMnO4It is molten Liquid；Wherein, soluble salt solutions F is low price manganese salt, and soluble salt solutions E is high price manganese salt；Soluble manganese salting liquid F is used to also Former soluble manganese salting liquid E is (for example, KMnO4Solution) value Mn obtain manganese dioxide；The surfactant can be ten Dialkyl sulfonates.
Preparation method according to the present invention, the solution of the presoma containing lithium-contained composite oxide and soluble manganese salt is molten Liquid E is (for example, KMnO4Solution) it is mixed and stirred for uniformly, surfactant sodium dodecyl base sodium sulfonate, the surface-active being then added Agent forms layered liquid crystal under a certain concentration, i.e. the polar head of active agent molecule mutually associates towards polarizable medium, apolar chain Layered micella is aligned, reaction is limited in specific space and carried out by lameller micelles, ensure that the specific shape of synthetic material Looks.Then the heating of obtained mixed solution is reacted, then the reactant of reaction and part solubility manganese salt F is carried out instead It answers, wherein the soluble manganese salting liquid F intervals, until the amount of the soluble manganese salting liquid F is used up.
Preparation method according to the present invention, wherein be added in first reaction or repetition first reaction The dosage of part soluble manganese salting liquid F and the mass ratio of the surfactant are (0.04-0.2): 1.
Preferably, LiOH solution, soluble salt solutions, KMnO4The dosage of solution E, oxidant and soluble manganese salting liquid F Molar ratio can be 1:(0.4-0.5): (0.01-0.08): (2-15): (0.015-0.12), preferably 1:(0.46-0.5): (0.04-0.06): (3-10): (0.06-0.09).
Preparation method according to the present invention, it is 190-210 DEG C that the condition of first reaction, which includes: temperature, time 1-3 Hour；Wherein, in the present invention, the condition of second reaction can be identical as the condition of first reaction；Therefore, described The condition of second reaction includes: that temperature is 190-210 DEG C, time 1-3h；
Similarly, the operation of the first reaction and the second reaction is repeated, that is, carry out third reaction and the 4th reaction, wherein third React identical as the condition of first reaction, the 4th reaction is identical as the condition of second reaction, that is, the third The condition of reaction includes: that temperature is 190-210 DEG C, time 1-3h；It is 190- that the condition of 4th reaction, which includes: temperature, 210 DEG C, time 1-3h.
Preferably, it is described first reaction condition include: temperature be 195-205 DEG C, more preferably 200 DEG C, time 1-2 Hour.Similarly, it is 195-205 DEG C that the condition of second reaction, which includes: temperature, and more preferably 200 DEG C, the time is 1-2 hours； The condition of third reaction includes: that temperature is 195-205 DEG C, and more preferably 200 DEG C, the time is 1-2 hours；The condition of 4th reaction Include: temperature be 195-205 DEG C, more preferably 200 DEG C, the time be 1-2 hours.
Preferably, the rate that the LiOH solution is added dropwise can be 0.5-2 ml/min.
Preferably, repeat the first reaction and second reaction, that is, carry out third reaction and the 4th reaction, be related to by Solution F points of several subparticipations are into reaction, wherein and in each section, there is no particular limitation for the specific dosage of solution F, Solution F is participated in into reaction by different level as long as meeting, until as needed in batch by the soluble manganese salting liquid Addition；For example, in the present invention, it is preferred to, the condition of the soluble manganese salting liquid F intervals include: every The amount of charging in 1.5-2.5 hours is 0.01VF-0.1VF, wherein VFFor F solution original bulk volume (unit, ml)；In the present invention, Pass through the above-mentioned reaction process of strict control, wherein solution F can need to be adjusted according to experiment, can obtain stacked in multi-layers Made of positive electrode material, and the positive electrode material of different conducting bases and lithium-contained composite oxide can be obtained.
Preparation method according to the present invention, lauryl sodium sulfate affect pattern, the ruler of prepared positive electrode material Very little and size.
Preparation method according to the present invention, wherein after reaction, precipitating is filtered, it is anti-with deionized water and ethyl alcohol It is multiple to clean for several times, dried for standby, that is, be heat-treated, wherein the temperature and time of heat treatment is not particularly limited, as long as will Reactant drying.Under preferable case, the condition of the heat treatment includes: that temperature is 80-120 DEG C, and the time is 5-24 hours, It is highly preferred that temperature is 90-110 DEG C, the time is 8-20 hours.
Preparation method according to the present invention, the reaction (hydro-thermal reaction) carries out under stirring conditions, for stirring Equipment is not particularly limited, for example, can be agitating paddle, mixing pump etc.；Stirring rate is also not particularly limited, for example, can Think 50-500 revs/min.
The equipment of preparation method according to the present invention, the reaction (hydro-thermal reaction) is not particularly limited, for example, can be It is carried out in hydrothermal reaction kettle.
Preparation method according to the present invention, wherein the partial size of the positive electrode material layer is 50nm-3 μm.
Preparation method according to the present invention, wherein the length of the lithium-contained composite oxide lamella is 100nm-2 μm, often A lithium-contained composite oxide lamella with a thickness of 10nm-250nm, each MnO2To matrix lamella with a thickness of 10nm-200nm；Preferably, the length of the lithium-contained composite oxide lamella is 200nm-1 μm, each composite oxygen containing lithium Compound lamella with a thickness of 10nm-200nm, each MnO2Conducting base lamella with a thickness of 10nm-160nm；Further Preferably, the length of the lithium-contained composite oxide lamella is 300-600nm, the thickness of each lithium-contained composite oxide lamella Degree is 10nm-150nm, each MnO2Conducting base lamella with a thickness of 10nm-100nm.
Preparation method according to the present invention, wherein the composition of the lithium-contained composite oxide lamella may include Li1+ xL1-y-zMyNzO2And/or LiNi0.5-x1Mn1.5-y1Ax1+y1O4；
Wherein, at least one of L, M, N Li, Co, Mn, Ni, Al, Mg, Ga, Ti, Cr, Cu, Zn and Mo, -0.1≤x ≤ 0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0；
Wherein, -0.1≤x1≤ 0.5,0≤y1In≤1.5, A Li, Co, Al, Mg, Ca, Ti, Mo, Cr, Cu and Zn extremely Few one kind.
Another preferred embodiment according to the present invention, a kind of preparation method of positive electrode material include following step It is rapid:
LiOH solution is added drop-wise in soluble salt solutions by (1 '), then mixes obtained mixture with oxidant, Obtain the solution of the presoma containing lithium-contained composite oxide；
(2 ') KMnO is prepared4Solution E；
(3 ') soluble manganese salting liquid F is prepared；
(4 ') in the presence of surfactant, by a part of KMnO4Solution E and a part of soluble manganese salting liquid F are mixed It closes and stirs evenly and the first reaction occurs and obtain a part of MnO2Lamella；Before again by a part containing lithium-contained composite oxide The solution for driving body carries out the second reaction and in obtained a part of MnO2The upper surface of lamella and following each stacking a part contain lithium Composite oxides lamella；
Then, then in the presence of surfactant, by another part KMnO4Solution E and another part solubility manganese salt Solution F is mixed and stirred for uniformly and occurs third reaction and in the upper surface of obtained a part of lithium-contained composite oxide lamella heap Folded another part MnO2Lamella；The solution that another part is contained to the presoma of lithium-contained composite oxide again carries out the 4th reaction simultaneously In obtained another part MnO2The upper surface of lamella stacks another part lithium-contained composite oxide lamella；
Sequence according to this, makes MnO2Lamella is successively superimposed growth with lithium-contained composite oxide lamella, until stopping as needed Feed and then stop reaction or as needed until using up the amount of the soluble manganese salting liquid F.
Fourth aspect, the present invention provides a kind of anodes, wherein the anode contains positive electricity described above Positive electrode material made from pole material or method described above.
Positive electrode material proposed by the present invention removes glue process after all-solid-state battery piece is made, by high temperature, without conduction Agent is free of binder, is pure electrode material piece.
Preferably, the anode also contains solid electrolyte；It is described relative to the positive electrode material of 100 parts by weight The content of solid electrolyte is 5-30 parts by weight；Wherein, the specific weight of the solid electrolyte is not particularly limited, and is normal Raw material is advised, can be selected according to demand.
According to the present invention, there is no any special restriction to the electrode current collecting body, the electricity of this field routine can be used Pole collector, for example, copper foil, aluminium foil etc., thickness for example can be 1-100 μm.
According to the present invention, when preparing all-solid-state lithium-ion battery anode slice using positive electrode material of the invention, made Method is not particularly limited, and under preferable case, which is suitable for the tape casting and prepares all-solid-state lithium-ion battery Positive plate, also, when preparing all-solid-state lithium-ion battery anode slice using the tape casting using the positive electrode material, without addition Conductive agent.
5th aspect, the present invention provides a kind of all-solid-state batteries, wherein the all-solid-state battery includes: anode, electrolyte Layer and cathode, the battery electrode just extremely described above.
According to the present invention, the cathode of above-mentioned battery may be the cathode of this field routine, such as can adhere to for surface There is the negative current collector of lithium metal and optional polymeric matrix.The negative current collector can be for example copper foil, copper mesh etc..
The present invention will be described in detail by way of examples below.
Charge-discharge test method:
By detected materials such as P1, C1, binder polyvinyl butyral PVB, plasticiser dibutyl phthalate DBP It is added in the mixed solution of ethyl alcohol and toluene, after being uniformly dispersed, slurry is uniformly cast on basis material, dry, cut out It is cut into the positive plate of diameter 1.3cm, above-mentioned positive plate and similar approach are cast the inorganic solid electrolyte piece lamination cut out, After high temperature is except glue, then it is compound with lithium piece, all-solid lithium-ion battery is made in cold pressing.
Measure battery charge-discharge performance under 0.5C multiplying power.
Embodiment 1
The present embodiment indicates that the positive battery material and battery being prepared using preparation method of the invention Anode and all-solid-state battery.
(1) Co (NO of 0.5L 0.8mol/L is prepared3)2Solution and 1L 4mol/L LiOH solution, by LiOH solution by It is added dropwise to Co (NO3)2In solution, after LiOH solution is added dropwise to complete, it is slow added into 50g 30%H2O2Aqueous solution obtains The solution D of presoma containing lithium-contained composite oxide, wherein the rate that LiOH solution is added dropwise is 1 ml/min；
(2) 0.024mol 3.8g KMnO is weighed4Solution is dissolved in 100ml deionized water, is configured to solution E；
(3) 0.36mol/L Mn (NO is prepared3)2Solution 100ml is marked as solution F；
(4) it is added in hydrothermal reaction kettle after mixing the solution D of the presoma containing lithium-contained composite oxide with E, 200 Rev/min stirring condition under stir, it is to be mixed uniformly after be added 250g lauryl sodium sulfate until completely dissolved will be upper It states solution and is heated to 200 DEG C, after reacting 2h, 20ml solution F is added into autoclave by feeding warehouse, continue to add after being spaced 2h 20ml solution F, repeatedly until solution F is added.200 DEG C of reactions for 24 hours, gained are precipitated and is filtered later, and deionized water is multiple It is cleaned and dried.
As a result it can get the positive electrode P1；The conductivity for testing P1 is as shown in table 1；It can also obtain containing this just The all solid lithium cobalt positive plate P11 of pole material P1, and the all-solid-state battery P111 containing positive plate P11.
Fig. 1 is the SEM electromicroscopic photograph of positive electrode material prepared by the embodiment of the present invention 1；As can be seen from the picture, it prepares Material presentation layer layer heap stack structure out, lamella LiCoO2Between stacked spaced apart have MnO2Layer.Wherein LiCoO2Leaf length is 450nm or so.
Fig. 2 and Fig. 3 is before positive electrode material prepared by the embodiment of the present invention 1 charges and 200 0.5C charge and discharge follow Anode section SEM schemes after ring.As can be seen from Fig., after undergoing 200 circulations, which has still maintained initial layer Layer heap stack structure.
Embodiment 2
The present embodiment indicates that the positive battery material and battery being prepared using preparation method of the invention Anode and all-solid-state battery.
(1) 14.7g 0.06mol Mn (CH is weighed3COO)2﹒ 4H2O is dissolved in 40ml deionized water, is configured to solution A；
(2) it weighs 9.6g ammonium carbonate to be dissolved in 20ml deionized water, is configured to solution B；
(3) 67.2g 0.27mol Co (CH is weighed3COO)2﹒ 4H2O is dissolved in 100ml deionized water, by 113.2g LiOH ﹒ H2O is dissolved in solution in 100ml deionized water, and above-mentioned LiOH solution is added dropwise to Co (CH dropwise3COO)2In solution, to complete After portion is added, it is slowly added to 35g 30%H2O2Aqueous solution obtains the solution M of the presoma containing lithium-contained composite oxide, In, the rate that LiOH solution is added dropwise is 1.2 ml/mins；
(4) the azeotropic point mixed solution 500ml of diglycol DEG and water are prepared, wherein VolDEG:VolH2O=40: 1；By heat in solution addition 1L three-neck flask to 120 DEG C.Under the conditions of being slowly stirred while solution is added at 100 revs/min A4ml and solution B 2ml；After reacting 0.5h, 200 DEG C are raised the temperature to, part is slowly added to and contains lithium-contained composite oxide The solution M 20ml of presoma temperature is reduced to 120 DEG C, continuously adds solution A 4ml and solution B after reacting 2h 2ml raises the temperature to 200 DEG C after reacting 0.5h again.Top-operation is repeated, until above-mentioned preparation solution adds. After being added dropwise to complete, continue heating stirring for 24 hours.After reaction, precipitating is filtered, is cleaned repeatedly with deionized water and ethyl alcohol For several times.110 DEG C of dried for standby.
(5) by above-mentioned product in 350 DEG C of heat treatment 5h.
As a result it can get the positive electrode P2；The conductivity for testing P2 is as shown in table 1；It can also obtain containing this just The all solid lithium cobalt positive plate P22 of pole material P2, and the all-solid-state battery P222 containing positive plate P22.
Embodiment 3
The present embodiment indicates that the positive battery material and battery being prepared using preparation method of the invention Anode and all-solid-state battery.
(1) NiCl of 0.5L 0.64mol/L is prepared2With 0.16mol/L Co (NO3)2Solution and 1L4mol/L LiOH LiOH solution is added dropwise to Co (NO by solution dropwise3)2In solution, after LiOH solution is added dropwise to complete, it is slow added into 15g The solution D of the presoma containing lithium-contained composite oxide can be obtained to fully reacting in NaClO after mixing evenly, wherein The rate that LiOH solution is added dropwise is 2 ml/mins；
(2) 0.024mol 3.8g KMnO is weighed4Solution is dissolved in 100ml deionized water, is configured to solution E；
(3) 0.36mol/L Mn (NO is prepared3)2Solution 100ml is marked as solution F；
(4) it is added in hydrothermal reaction kettle after mixing the solution D of the presoma containing lithium-contained composite oxide with E, 150 Rev/min stirring condition under stir, it is to be mixed uniformly after be added 250g lauryl sodium sulfate until completely dissolved will be upper It states solution and is heated to 200 DEG C, after reacting 2h, 20ml solution F is added into autoclave by feeding warehouse, continue to add after being spaced 2h 20ml solution F, repeatedly until solution F is added.200 DEG C of reactions for 24 hours, gained are precipitated and is filtered later, and deionized water is multiple It is cleaned and dried.
As a result it can get the positive electrode P3；The conductivity for testing P3 is as shown in table 1；It can also obtain containing this just The all solid lithium cobalt positive plate P33 of pole material P3, and the all-solid-state battery P333 containing positive plate P33.
Embodiment 4
The present embodiment indicates that the positive battery material and battery being prepared using preparation method of the invention Anode and all-solid-state battery.
(1) NiCl of 0.5L 0.3mol/L is prepared2、0.3mol/L MnCl2With 0.3mol/L Co (NO3)2Mixing it is molten Liquid and 1L 4mol/L LiOH solution, LiOH solution is added dropwise to dropwise in above-mentioned mixing salt solution, is added dropwise to LiOH solution After the completion, it is slow added into 16.8g NaClO, to fully reacting, is can be obtained after mixing evenly containing lithium-contained composite oxide Presoma solution D, wherein LiOH solution be added dropwise rate be 1.5 ml/mins；
(2) 0.02mol 3.8g KMnO is weighed4Solution is dissolved in 100ml deionized water, is configured to solution E；
(3) 0.3mol/L Mn (NO is prepared3)2Solution 100ml is marked as solution F；
(4) it is added in hydrothermal reaction kettle after mixing the solution D of the presoma containing lithium-contained composite oxide with E, 250 Rev/min stirring condition under stir, it is to be mixed uniformly after be added 250g lauryl sodium sulfate until completely dissolved will be upper It states solution and is heated to 200 DEG C, after reacting 2h, 20ml solution F is added into autoclave by feeding warehouse, continue to add after being spaced 2h 20ml solution F, repeatedly until solution F is added.200 DEG C of reactions for 24 hours, gained are precipitated and is filtered later, and deionized water is multiple It is cleaned and dried.
As a result it can get the positive electrode P4；The conductivity for testing P4 is as shown in table 1；It can also obtain containing this just The all solid lithium cobalt positive plate P44 of pole material P4, and the all-solid-state battery P444 containing positive plate P44.
Embodiment 5
The present embodiment indicates that the positive battery material and battery being prepared using preparation method of the invention Anode and all-solid-state battery.
(1) Ni (NO of 0.5L 0.68mol/L is prepared3)2、0.12mol/L Co(NO3)2With 0.04mol/LAl (NO3)3's Mixed solution and 1L 4mol/L LiOH solution, LiOH solution is added dropwise to dropwise in above-mentioned mixing salt solution, molten to LiOH After liquid is added dropwise to complete, it is slow added into 17.7g NaClO, to fully reacting, is can be obtained after mixing evenly containing compound containing lithium The solution D of the presoma of oxide, wherein the rate that LiOH solution is added dropwise is 1 ml/min；
(2) 0.03mol 4.7g KMnO is weighed4Solution is dissolved in 100ml deionized water, is configured to solution E；
(3) 0.45mol/L Mn (NO is prepared3)2Solution 100ml is marked as solution F；
After the solution D of presoma containing lithium-contained composite oxide is mixed with E be added hydrothermal reaction kettle in, 150 turns/ It is stirred under the stirring condition of minute, uniformly rear addition 250g lauryl sodium sulfate to be mixed until completely dissolved will be above-mentioned molten Liquid is heated to 200 DEG C, and after reacting 2h, 20ml solution F is added into autoclave by feeding warehouse, continues to add 20ml after being spaced 2h Solution F, repeatedly until solution F is added.200 DEG C of reactions for 24 hours, gained are precipitated and is filtered later, and deionized water is cleaned multiple times It is dry.
As a result it can get the positive electrode P5；The conductivity for testing P5 is as shown in table 1；It can also obtain containing this just The all solid lithium cobalt positive plate P55 of pole material P5, and the all-solid-state battery P555 containing positive plate P55.
Comparative example 1
Prepare the Co (NO of 0.5L 0.8mol/L3)2The LiOH solution of solution and 1L 4mol/L, dropwise by LiOH solution It is added dropwise to Co (NO3)2In solution, after LiOH solution is added dropwise to complete, it is slow added into the H of 50g 30%2O2Aqueous solution, wherein The rate that LiOH solution is added dropwise is 1 ml/min；Above-mentioned acquired solution is added in hydrothermal reaction kettle, in 200 DEG C of hydro-thermal reactions Sediment is filtered out for 24 hours, and deionized water is cleaned for several times, 100 DEG C of drying.
As a result it can get electrode material C1；The conductivity for testing C1 is as shown in table 1；It can also obtain containing the positive electrode The all solid lithium cobalt positive plate C11 of C1, and the all-solid-state battery C111 containing positive plate C11.
Table 1
Fig. 4 is the song of positive electrode P1 prepared by the embodiment of the present invention 1 and cobalt acid lithium sintered sheets C1 in 0.5C charge and discharge Line comparison diagram.Figure 4, it is seen that positive electrode P1 prepared by the present invention, has stacked in multi-layers structure, lamella LiCoO2It Between stacked spaced apart have MnO2Layer exists since the positive electrode removes glue process and the positive electrode in the case where undergo high-temperature oxygen atmosphere Still electronic conductivity with higher when high-voltage charge, without additional addition conductive agent, therefore, as all solid lithium When cobalt positive plate P11, when 0.5C discharges, discharge capacity is up to 142mAh/g；And common lithium cobalt is prepared just by the tape casting Pole piece C11 is heat-treated under high temperature oxygen atmosphere because need to withstand, and is not suitable for the conductive agent of the system, thus is put in 0.5C When electric, discharge capacity only has 106mAh/g.This is because removing glue mistake in high temperature using the battery electrode of positive electrode of the invention Cheng Zhong, partially electronically conductive matrix MnO2It is decomposed into Mn2O3, but handled by 4.0V or more oxidation at voltages for the first time, it is completely converted into MnO2, the electronic conductivity of material is not influenced.
In addition, as known from Table 1, the positive electrode P1-P5 that preparation method through the invention obtains has good electronics Conductivity can satisfy all-solid lithium-ion battery using the positive plate P11-P55 of positive electrode electronic conductivity itself and fill Electric discharge demand is not required to additionally add conductive agent.
In addition, the positive electrode P1-P5 that preparation method through the invention obtains, and can also obtain containing the anode The all solid lithium cobalt positive plate P11-P55 of material P1-P5, and the all-solid-state battery P111- containing positive plate P11-P55 P555, wherein the electrical conductive activities of all-solid-state battery P111-P555 are higher and high rate performance is excellent, solve currently used Carbon class, metal class conductive agent, the problem of oxidation reaction can occur under high-temperature oxygen atmosphere, lose electrical conductive activities；Meanwhile Also traditional lithium-ion battery positive electrode is solved not plus when conductive agent, the problem of material forthright difference again；In addition, the prior art In, for the positive electrode with oxidisability, for example, LiCoO2, NCA, NCM, LiNi0.5Mn1.5O4Deng not positive with these What material matched is suitable for the conductive agent of the tape casting preparation all-solid lithium-ion battery, and therefore, the present invention provides one kind to have The solution of effect, that is, positive electrode of the invention can be directly used for the preparation of positive plate, without adding conductive agent.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (18)

1. a kind of positive electrode material, which is characterized in that the positive electrode material includes MnO2Conducting base lamella and composite oxygen containing lithium Compound lamella, the MnO2Conducting base lamella and the lithium-contained composite oxide lamella are alternately stacked, the composite oxygen containing lithium The composition of compound lamella includes Li1+xL1-y-zMyNzO2And/or LiNi0.5-x1Mn1.5-y1Ax1+y1O4；
Wherein, at least one of L, M, N Li, Co, Mn, Ni, Al, Mg, Ga, Ti, Cr, Cu, Zn and Mo, -0.1≤x≤ 0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0；
Wherein, -0.1≤x1≤ 0.5,0≤y1At least one in≤1.5, A Li, Co, Al, Mg, Ca, Ti, Mo, Cr, Cu and Zn Kind.
2. positive electrode material according to claim 1, wherein the positive electrode material has one or more repetitions single Member, wherein each described repetitive unit is with MnO2Conducting base lamella is as support construction, and in the MnO2Conductive base The upper surface of body lamella is stacked with the lithium-contained composite oxide lamella and the MnO with following2Conducting base lamella is less than institute State lithium-contained composite oxide lamella.
3. positive electrode material according to claim 1 or 2, wherein the length of the lithium-contained composite oxide lamella is 100nm-2 μm, each lithium-contained composite oxide lamella with a thickness of 10nm-250nm, each MnO2Conducting base piece Layer with a thickness of 10nm-200nm；
Preferably, the length of the lithium-contained composite oxide lamella is 200nm-1 μm, each lithium-contained composite oxide lamella With a thickness of 10nm-200nm, each MnO2Conducting base lamella with a thickness of 10nm-160nm；
It is further preferred that the length of the lithium-contained composite oxide lamella is 300-600nm, each combined oxidation containing lithium Object lamella with a thickness of 10nm-150nm, each MnO2Conducting base lamella with a thickness of 10nm-100nm.
4. positive electrode material according to claim 1 or 3, wherein the partial size D50 of the positive electrode material is 50nm-3 μ m。
5. positive electrode material described in any one of -4 according to claim 1, wherein with the total weight of the positive electrode material On the basis of, the MnO2The content of conducting base is 5-40 weight %, preferably 10-25 weight %, more preferably 10-15 weight Measure %.
6. a kind of preparation method of positive electrode material, which is characterized in that method includes the following steps:
(1) in the presence of 50-160 DEG C, mixed solvent, the first reaction of manganese carbonate raw material progress will be prepared and obtain lamella containing manganese carbonate Solution E；In 180-250 DEG C, solution E, the solution of the presoma containing lithium-contained composite oxide is carried out second and is reacted To the solution F containing lithium-contained composite oxide lamella；Again in solution F, the first reaction, the second reaction are repeated；Sequence according to this, makes Manganese carbonate lamella is successively superimposed growth with lithium-contained composite oxide lamella；Manganese carbonate raw material is prepared in first reaction every time It measures identical or different；The amount of the solution of the presoma containing lithium-contained composite oxide is identical or not in second reaction every time Together；
(2) product of step (1) is subjected to high-temperature heat treatment；
The mixed solvent include water and containing hydroxyl and can azeotrope with water organic solvent.
7. according to the method described in claim 6, wherein, the solution F containing lithium-contained composite oxide lamella is by LiOH Solution is added drop-wise in soluble salt solutions, is then obtained by mixing obtained mixture and oxidant, wherein it is described can Dissolubility salting liquid is to contain one in cobalt salt, nickel salt, manganese salt, aluminium salt, magnesium salts, gallium salt, titanium salt, chromic salts, mantoquita, zinc salt and molybdenum salt Kind or a variety of aqueous solutions；The oxidant is H2O2And/or sodium hypochlorite；Preferably, the soluble salt solutions are to contain Co (NO3)2、NiCl2、Ni(NO3)2、MnCl2With Al (NO3)3One of or a variety of aqueous solutions；
Preferably, preparing manganese carbonate raw material includes manganese salt solution A and carbonate solution B；
Preferably, the manganese salt solution A is to contain manganese oxalate, manganese acetate, manganese chloride, one of manganese nitrate and manganese sulfate or more The aqueous solution of kind；The carbonate solution B is the aqueous solution containing ammonium carbonate and/or ammonium hydrogen carbonate；It is described containing hydroxyl and The organic solvent of energy azeotrope with water is at least one of diglycol, ethylene glycol, triethylene glycol and tetraethylene glycol.
8. method according to claim 6 or 7, wherein it is described containing hydroxyl and can azeotrope with water organic solvent with The volume ratio of the dosage of water is (35-45): 1；Wherein, described first reacts or repeats the portion being added in first reaction The volume ratio of the total dosage and the mixed solvent of dividing the solution A and the part solution B is 2:(50-500)；Described second The solution of presoma containing lithium-contained composite oxide described in the part being added in reaction or repetition second reaction Dosage and the volume ratio of the mixed solvent are 1:(5-100).
9. according to the method described in claim 6, wherein, in step (1), the condition of first reaction includes: in temperature 1min-1h is reacted under the conditions of being 50-160 DEG C；The condition of second reaction includes: anti-under the conditions of temperature is 180-250 DEG C Answer 30min-2h；
In step (2), the condition of the high-temperature heat treatment includes: that temperature is 300-500 DEG C, time 5-24h.
10. a kind of preparation method of positive electrode material, which is characterized in that this method comprises:
In the presence of 190-210 DEG C, surfactant, the first reaction is occurred into for the raw material for preparing manganese dioxide and is obtained containing MnO2Piece The solution G of layer, in solution G, the solution of the presoma containing lithium-contained composite oxide carries out the second reaction and obtains containing containing lithium The Solution H of composite oxides lamella；Again in Solution H, the first reaction, the second reaction are repeated；Sequence according to this, makes manganese dioxide piece Layer is successively superimposed growth with lithium-contained composite oxide lamella；The amount phase of the raw material of manganese dioxide is prepared in first reaction every time It is same or different；The amount of the solution of the presoma containing lithium-contained composite oxide is identical or different in second reaction every time；
Wherein, the raw material for preparing manganese dioxide includes soluble manganese salting liquid E and soluble manganese salting liquid F, wherein described Soluble manganese salting liquid E be include Mn+n, and the soluble manganese salting liquid E of n > 4；The soluble manganese salting liquid F be include Mn+m, and the soluble manganese salting liquid F of m≤3.
11. according to the method described in claim 10, wherein, the solution of the presoma containing lithium-contained composite oxide is will LiOH solution is added drop-wise in soluble salt solutions, is then obtained by mixing obtained mixture and oxidant, wherein institute Stating soluble salt solutions is containing in cobalt salt, nickel salt, manganese salt, aluminium salt, magnesium salts, gallium salt, titanium salt, chromic salts, mantoquita, zinc salt and molybdenum salt One or more aqueous solutions；The oxidant is H2O2And/or sodium hypochlorite；
Preferably, the soluble manganese salting liquid F is the manganese chloride containing manganese oxalate, manganese acetate, one in manganese nitrate and manganese sulfate Kind or a variety of aqueous solutions；The surfactant is dodecyl sodium sulfate；The soluble manganese salting liquid E is KMnO4It is molten Liquid.
12. method described in 0 or 11 according to claim 1, wherein first reaction repeats institute in first reaction The mass ratio of the dosage of the part soluble manganese salting liquid F and surfactant of addition is (0.04-0.2): 1.
13. according to the method for claim 12, wherein the condition of the soluble manganese salting liquid F intervals includes: every Every 1.5-2.5 hours charging amount be (0.01VF-0.1VF) ml, wherein VFFor F solution original bulk volume.
14. it is 190-210 DEG C that the condition of first reaction, which includes: temperature, according to the method described in claim 10, wherein, Time is 1-3h；It is 190-210 DEG C that the condition of second reaction, which includes: temperature, time 1-3h.
15. the method according to any one of claim 6-9 or 10-14, wherein the lithium-contained composite oxide piece Layer length be 100nm-2 μm, each lithium-contained composite oxide lamella with a thickness of 10nm-250nm, each MnO2 Conducting base lamella with a thickness of 10nm-200nm；
Preferably, the length of the lithium-contained composite oxide lamella is 200nm-1 μm, each lithium-contained composite oxide lamella With a thickness of 10nm-200nm, each MnO2Conducting base lamella with a thickness of 10nm-160nm；
It is further preferred that the length of the lithium-contained composite oxide lamella is 300-600nm, each combined oxidation containing lithium Object lamella with a thickness of 10nm-150nm, each MnO2Conducting base lamella with a thickness of 10nm-100nm；
It is further preferred that the composition of the lithium-contained composite oxide lamella includes Li1+xL1-y-zMyNzO2And/or LiNi0.5-x1Mn1.5-y1Ax1+y1O4；
Wherein, at least one of L, M, N Li, Co, Mn, Ni, Al, Mg, Ga, Ti, Cr, Cu, Zn and Mo, -0.1≤x≤ 0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0；
Wherein, -0.1≤x1≤ 0.5,0≤y1At least one in≤1.5, A Li, Co, Al, Mg, Ca, Ti, Mo, Cr, Cu and Zn Kind.
16. a kind of anode, which is characterized in that the anode contains described in any one of claim 1-5 just Positive electrode material made from method described in any one of electrode material or claim 6-9 or 10-15.
17. a kind of all-solid-state battery, which is characterized in that the all-solid-state battery includes: anode, electrolyte layer and cathode, it is described just Extremely anode described in claim 16.
18. all-solid-state battery according to claim 17, wherein the cathode is the cathode collection that surface is attached with lithium metal Fluid.
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