CN102376951A - Method for synthesizing metal compound by using carbon thermal reduction method - Google Patents
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Abstract
The invention discloses a method for synthesizing a metal compound by using a carbon thermal reduction method. The method comprises the following steps of: a, preparing for reactants including one or more metal compounds, a phosphate salt ion source and a mixture formed by at least one reduction carbon; b, enabling the reactants to form a mixture; and c, heating the mixture, synthesizing a phosphoric acid metal salt product, and controlling the quantity of the reduction carbon to achieve the condition that at least one metal can be changed into an oxidization state in the heating without being completely reduced into simple substances. The invention has the advantages that: the method can obtain a lithium-containing electrode material with better capacity and no remarkable capacity attenuation; and the method has lower cost and is convenient for batch production.
Description
Technical field:
The present invention relates to a kind of method of synthetic metallic compound, especially relate to the method for the synthetic metallic compound of a kind of carbothermic method.
Background technology:
In recent years, lithium ion battery has become a kind of effective, and and attractive energy storage device.Generally speaking, lithium battery is processed by the electric core that contains active material.This electric core is by negative material, and positive electrode and electrolyte are formed.That is to say that oxidation reaction takes place negative pole in discharge, the anodal reduction reaction that in discharge, takes place.
Lithium battery has one to insert negative pole, like lithium metal oxide, and coke or graphite.It is gone in battery into the electrochemistry coupling with the insertion positive pole that contains lithium.Battery is not recharged under initial condition.Battery must be recharged before transmitting electrochemical energy.In charging process, lithium ion is transferred to negative pole from the positive pole that contains lithium.In discharge process, lithium ion is transferred to positive pole from negative pole.In charging afterwards, lithium ion has been transferred to negative pole again.Therefore along with charge and discharge cycles each time, lithium ion shifts between electrode.But the battery of this recharge does not have release metal ions, therefore is called as rechargeable lithium ion battery or rocking chair battery.
Positive electrode active materials comprises cobalt acid lithium, LiMn2O4 and lithium nickelate.The synthetic cost of cobalt acid lithium is higher relatively.The synthetic relatively difficulty and complicated of lithium nickelate.The two kinds of materials in relative front, the synthetic cost of LiMn2O4 is lower.Yet all there is shortcoming in above-mentioned three kinds of materials when using in battery as electrochemical material.When they used in battery, positive electrode was in the charge and discharge cycles process, and charging capacity can decline to a great extent.And the initial capacity that material can be used is lower than theoretical capacity.Initial capacity will significantly descend in the circulation for the first time, and what in ensuing circulation, can descend is severe more.In battery recycled, it was reversible having only the lithium of 0.5 unit in the lithium nickelate of a unit.
People have attempted a variety of methods and have removed to reduce capacity attenuation, yet in daily use, the relative capacity of transition alkali metal compound known today is lower.Therefore, go for a kind of capacity better and do not have an obvious capacity attenuation contain the lithium electrode material comparison difficulty that just seems.
Summary of the invention:
Technical problem to be solved by this invention provides a kind of capacity better and do not have an a kind of method of producing electrode active material that contains the lithium electrode material of obvious capacity attenuation.
In order to solve the problems of the technologies described above, the present invention realizes through following technical scheme:
The method of the synthetic metallic compound of this carbothermic method is characterized in that, may further comprise the steps:
(a) preparation of reactant: the mixture that comprises one or more metallic compounds, phosphate ion source, at least a reduction carbon composition;
(b) make reactant is formed mixture;
(c) add hot mixt, synthetic phosphate metal product salt under uniform temperature and time, the amount of reduction carbon should be controlled at and can make a kind of metal pine for becoming oxidation state adding at least, and does not make it be reduced into simple substance fully.
Further, the metallic compound in the said step (a) comprises a kind of transistion metal compound.
Further, the metallic compound in the said step (a) comprises the compound of tin.
Further, the reduction carbon in the said step (a) comprises DIC.
Further, the reduction carbon in the said step (a) comprises organic carbon.
Again further, said organic carbon is pined for decomposing adding, and some form with reducing agent in reaction exists.
Again further, contain carbohydrate and sucrose in the reduction carbon carbon source in the said step (a).
Again further, the compound in the said step (a) is to contain a kind of lithium compound.
Further, the heating-up temperature in the said step (c) is between 400 ℃ to 1200 ℃.
Contain transition metal oxide and phosphate transition metal oxide in the product in the said step (c).
Compared with prior art, usefulness of the present invention is: this method can obtain a kind of capacity better and do not have an obvious capacity attenuation contain the lithium electrode material, and this synthetic method cost is lower, is convenient to produce in batches.
Description of drawings:
Fig. 1 is the SEM figure of instance 1 prepared phosphoric acid vanadium lithium of the present invention;
Fig. 2 is the XRD curve chart of instance 1 prepared phosphoric acid vanadium lithium of the present invention;
Fig. 3 is the size distribution curve figure of instance 1 prepared phosphoric acid vanadium lithium of the present invention;
Fig. 4 is the first charge-discharge curve chart of instance 1 prepared phosphoric acid vanadium lithium of the present invention.
Embodiment:
Describe the present invention below in conjunction with accompanying drawing and embodiment:
The method of the synthetic metallic compound of a kind of this carbothermic method is characterized in that, may further comprise the steps: (a) preparation of reactant: the mixture that comprises one or more metallic compounds, phosphate ion source, at least a reduction carbon composition; (b) make reactant is formed mixture; (c) add hot mixt, synthetic phosphate metal product salt under uniform temperature and time, the amount of reduction carbon should be controlled at and can make a kind of metal pine for becoming oxidation state adding at least, and does not make it be reduced into simple substance fully.The compound that metallic compound in the said step (a) comprises a kind of transistion metal compound and comprises tin; Reduction carbon comprises DIC and organic carbon; Said organic carbon is pined for decomposing adding, and some form with reducing agent in reaction exists; Contain carbohydrate and sucrose in the said reduction carbon carbon source; Compound in the step (a) is to contain a kind of lithium compound; Heating-up temperature in the said step (c) is between 400 ℃ to 1200 ℃; And contain transition metal oxide and phosphate transition metal oxide in the product in the step (c).Active material of the present invention has comprised a kind of alkali metal and a kind of metal that can be oxidized to the high price oxidation state at least.Other metal is selected (the 4th family in the periodic table of elements～11 families) from the group of containing transition metal can be other nontransition metal also, like Ti, and Bi, Pb etc.This active material can be synthetic with single-step method or multistep processes.In synthetic reaction, have a step at least, reduction carbon is used as reactant, and in this one, has at least a kind of metal to be reduced into oxidation state.On the one hand, metallic compound comprises transition metal, and on the other hand, metallic compound comprises nontransition metal such as Ti.
In synthetic reaction, the reducing agent of reducing metal derives from reduction carbon; On the one hand, the reduction carbon source is in by elemental carbon, and suitable carbon particulate is such as graphite, amorphous carbon, carbon black and other homologue; On the other hand, reduction carbon also can derive from organic precursor material or elemental carbon and organic precursor mixtures of material; Organic precursor material also is known as organic material in this patent.Organic precursor material or organic material are a kind ofly can resolve into the material with reproducibility carbon.
In addition, the reaction of metallic compound and carbon source is under the situation of no metallic reducing agent, to carry out.Whether that is to say that it is their oxidation state that metallic compound occurs that oxidation state is equivalent in the target product, no matter reacting is carbothermic reduction reaction, and carbon particle is easy to occupy the nucleus position of product crystal; Thereby it is little when carbon-free that crystal or particle can become, thereby little particle size is easier to form crystal tightly packedly generates high-quality active material; Carbon granule is dispersed in the entire reaction product, can form the product with good particle conductivity.This is used to the manufacturing of the high-quality active material under the carbon thermal reduction condition.
Reduction reaction possibly generally carried out in nonoxidizing atmosphere.Atmosphere possibly comprise reducing gas, like hydrogen.
The active material that also is embodied in of the present invention is a hybrid metal phosphate, optionally contains halogen or hydroxyl, and this hybrid metal phosphate contains at least a metal, and this metal can be oxidized to high oxidation state through peroxidization, tends to transition metal.
In addition, the phosphate radical salt group of above-described active material maybe be by other anionicsite or is all replaced; Nonpolar substitution ion comprises silicate, sulfate radical, germanic acid root, PO
3F
2-And PO
2F
2-The sulfo-ion that also has above ion; Such as, the D2EHDTPA root comprises PO
3S
3-, PO
2S
2 3-, POS
3 3-, PS
4 3-
The phosphate active material or the active material that possibly partially or completely replaced phosphate radical can be represented A with one general formula
aM
b(XY
4)
cZ
d, wherein,
A is Li, Na, and a kind of among the K or their mixture, 0＜a≤8,
1) M comprises one or more metals, and has at least a kind of metal to become high valence state through peroxidization, 1≤b≤3,
2) XY
4Be X ' O
4-xY '
x, X ' O
4-yY '
2y, X " and S
4In a kind of of group or they mixture.Wherein X ' is P, As, Sb, Si, Ge, V, a kind of among the S or their mixture, X " be P, As, Sb, Si, V, a kind of among the Ge or their mixture, Y ' is halogen S, N or their mixture.0≤x≤3，0＜y≤2，0＜c≤3，
3) Z is OH, halogen or their mixture.0≤d≤6
4) M, X, Y, Z, a, b, c, d, the selection of x and y must keep the electric neutrality of compound.
The present invention is mainly reflected in, and in the M containing element periodic table from 11 families of the 4th family to the two kinds or multiple transition metal, will embody in another is that M is by M ' M " form; wherein M ' comprises at least a transition metal from 11 families of the 4th family to the, and M " have at least a kind of element to derive from the periodic table of elements the 2nd, 3; 12,14 families, main embodiment comprises c=1; C=2, c=3 also comprises a≤1 and c=1; A=2 and c=1, a>=3 and c=3, this is sent out embodiment main and also comprises having the material similar with olivine structural.
In the above formula, A chooses Li, Na, and K, perhaps a kind of in their mixture, imbody is, A is Li, the mixture of Li and Na, the mixture of Li and K, perhaps Li, Na, K three's mixture; The another kind of embodiment be, A is Na, the perhaps mixture of Na and K, and a tendency and in 0.1～6, choosing preferably in 0.2～6 scope, is worked as c=1, and the scope of a is 0.1～3, preferably in 0.2～2 scope.Be typically, work as c=1, a is less than 1; Another kind is, works as c=1, and a is near 2; Work as c=2, a chooses in 1～6 scope 0.1～6; Work as c=3, a chooses in 2～6,3～6 scopes 0.1～6.
M comprises one or more metals; Wherein have at least a kind of metal to become high valence state through peroxidization; Typical performance is; The oxidation of at least a metal among the simultaneous M that alkali metal moves in the electroactive material, the amount of metal that can be oxidized in the active material have determined the alkali-metal amount that can be moved; These notions are used in some documents; As; By Fei Liao. Li Faming, the patent No. of issue on October 16th, 1984 is 4477541 United States Patent (USP), is invented by people such as Barks; The patent No. of issue on October 24th, 2000 is 6136472 United States Patent (USP), and the present invention unites with reference to above two patents.
M possibly contain a kind of metal, or two kinds of metals or multiple metal; When M was hybrid metal, M must keep the electric neutrality of active material in active material; (just all anionic positive charges and all cationic negative electrical charge balances.By complex element (M1, the clean chemical valence (V that M2...Mt) forms
M) can use formula V
M=V
M1b 1 + M2b 2 + ... + Mtb t, here, b
1+ b
2+ ...+b
t=1, and V
M1Be the oxidation state of M1, V
M2It is oxidation state of M2 or the like; (other component of the net charge of M and electrode active material will be discussed below).
At this, useful transition metal comprises Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg and their mixture.
The preferential transition metal series of selecting first row comprises Ti, V, Cr, Mn, Fe, Co, Ni, Cu and composition thereof.Fe particularly, Co, Mn, Cu, V, Cr and composition thereof, especially Fe, Co; Some situation, preferred transition metal mixture; Though these transition metal by various useful oxidation state, tend to use transition metal+divalent oxidation state here.
M also can be a nontransition metal or nonmetal; As, 2 family's elements, Be, Mg, Ca, Sr, Ba; 3 family's elements, Sc, Y, lanthanide series, La, Ce, Pr, Cd, Nd, Sm; The Zn of 12 families, Cd; The B of 13 families, Al, Ga, In, TI; 14 family's elements Si, Ge, Sn, Pb, the 15 elements A s of family, Sb, Bi; 16 element T e and composition thereof etc.; Nontransition metal comprises 2 families, 12 families, 13 families, 14 family's elements.The oxidation state of nontransition metal is+divalent or+3 valencys; The element of at least a+divalent oxidation state that nontransition metal comprises and the element of at least a+3 valency oxidation state; Nontransition metal is generally from Mg, Ca, and Zn, Sr, Pb, Cd, Sn, Ba selects among the Be, Al and composition thereof, Mg particularly, Ca, Zn, Ba, Al and composition thereof.
Further discuss, select b must keep the electrode active material electric neutrality; Generally, c=1, b are in the scope of 1-2, especially near 1.Work as c=2, b is in the scope of 2-3, especially near 2.If d=0, c is near 1, so 0.8≤a≤1.2,0.8≤b≤1.2.
XY
4Be X ' O
4-xY '
x, X ' O
4-yY '
2y, X " and S
4Or its mixture, wherein X ' is P, As, Sb, Si, Ge, S or its mixture.X " be P, As, Sb, Si, Ge or its mixture, typical, X ' and X " select P, Si and composition thereof respectively; Working as X ' is P, and Y ' is halogen (F); XY
4Restriction can not be a phosphate radical, silicate, sulfate radical, germanic acid root, PO
3F
2-And PO
2F
2-, also have the sulfo-ion of above ion.
When 0＜x＜3,0＜y＜4 o'clock, XY
4In the oxygen position have 1/2nd to be replaced by halogen.2.x and y is 0.
3. work as XY
4X ' possibly be P or Si when equaling X ' O.
Z is OH, halogen or both mixtures; 1. " d " equals zero, and 2.d is not equal to zero, and Z is by OH, F, and Cl, the group that Br or its mixture are formed, 3.Z is OH.4.Z be F or by F, OH, Cl, or the mixture formed of Br, the value of " d " possibly be 0.1～6 or 0.2～6, when c=1, the value of d maybe 0.1～3, and perhaps 0.2～2; C=1 for example, d=1, when c=2, the value of d maybe 0.1～6, and perhaps 1～6, when c=3, the value of d possibly be 0.1～6,2～6, perhaps 3～6.
M, X, the composition of Y and Z, and a, b, c, d, the value of x and y is all through selecting, keeping the electric neutrality of electrode active material, electric neutrality be exactly in the electrode active material amount of positive charge and negative electrical charge equal, XY
4In according to the kind of X, its valence state possibly be-2 ,-3, or-4.
Another kind of battery active material A
aM
bO
fComprise the transition alkali metal oxide, also can prepare that alkali metal possibly be selected from by Li, Na, K through method of the present invention; M possibly be a transition metal, transistion metal compound, or the mixture of transition metal and nontransition metal; A, b, the value non-zero of c, the combination back is to keep the electric neutrality of formula, and for example, transition metal M is selected from by Fe, Ni, Co, Mg, Fe, Ti, Zr, the crowd that Mo and V form.
With general formula A
aM
b(XY
4)
cZ
dThe active material of expression, reduction reaction not necessarily takes place in its raw material simultaneously in solid-state reaction.In course of reaction, one or more raw material are excessive, and in this case, the chemical combination of product supposes that various components all are useful.
Generally, any anion can generate the alkali metal initial reactant with alkali metal cation chemical combination, and is perhaps cloudy from M cation combination generation M initial reactant.Same, any cation can combine to generate the Z component reactant with halide or hydroxide radical anion, and any cation can be used as phosphate radical or similar XY
4The counterion of component, still, the material that can produce volatile byproducts is paid the utmost attention in the selection with reactant of counterion; Therefore, select ammonium salt, carbonate; Oxide, hydroxide is proper with similar material, the initial reactant with counterion tends to generate such as water; Ammonia, volatile byproducts such as carbon dioxide, they can be removed from reactant mixture easily.
It is worth noting active material A of the present invention
aM
b(XY
4)
cZ
dComprise mixed alkali metal A, hybrid metal B, blending ingredients Z with represent XY
4Phosphate radical.Another aspect of the present invention, phosphate radical can partly be replaced by half XY4 of family, and this is called as " phosphate replacement " or " modified phosphate ".Therefore, half XY4 of family among the present invention in the active material is that phosphate radical is by following material part or replacement fully, SO
4 2-, PO
3F
2-, PO
2F
2-, SiO
4 4-, arsenate, metaantimmonic acid root, vanadic acid root, germanic acid root.The oxygen anion of the above homologue of the active material among the present invention is partly or entirely replaced also by meaning by sulphur; In addition, sulfate radical can not be replaced by sulphur fully; For example, the D2EHDTPA root can be used for partly or entirely replacing the phosphate radical in the active material.These D2EHDTPA roots comprise PO
3S
3-, PO
2S
2 3-, POS
3 3-, PS
4 3-They are at Na, and Li is widely used in the K derivative.
For the synthetic active material that contains partially modified sulfate radical; Maybe be usually with replacing the above phosphate compounds of all or part of replacement of negative ion source; This substitution reaction is undertaken by stoichiometry; Provide to replace anionic initial reactant with above other initial reactant, the active material that contains the modified phosphate root reduces in non-oxidation by the method for above-mentioned discussion, and oxidation or reducing condition get off synthetic; Having under the situation of phosphate compounds, the compound that contains modification or replacement phosphate radical also can be the source of other component of active material; For example, alkali metal or hybrid metal possibly be the parts of modified phosphate salt compound.The stoichiometric proportion of article is through quantitative A, M, XY
4And the composition of Z decides, and in this case, some raw material can remain in the product at least, therefore raw-material accurate molar ratio need be provided.
Same, with general formula A
aM
bO
cThe active material of expression, all raw material provide a mol alkali metal A and b mole metal M at least in synthetic.
Alkali-metal source comprises many salt or lithium ion compound, Na, and K, Rb or Cs more possibly derive from Li, the compound of Na and K; Alkali metal should provide with the form of powder or particulate, and they have source widely aspect inorganic chemistry; Li for example, Na, potassium fluoride, chloride, bromide, iodide, nitrate; Nitrite, sulfate, sulfuric acid monohydric salt, sulphite, bisulfite, carbonate; Heavy carbonate, borate, phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, silicate; Stibate, arsenate, germanate, oxide, acetate, oxalates or the like.The hydroxide of above-claimed cpd or mixture also possibly be employed.Multiple alkali metal maybe be contained in the said mixture, therefore a kind of alkali metal mixed active material maybe be produced in the reaction.
Anion removes phosphate anion, and the halogen ion is outside the hydroxide ion; All provide by containing cationic compound or salt, this cation comprises that metal ion is like alkali metal, alkalinous metal; Transition metal, or other nontransition metal and complex cation are like ammonium and quaternary ammonium; The compound that contains phosphate anion possibly be phosphate, hydrophosphate or dihydric phosphate.Contain phosphate anion, the halogen ion, the original material of hydroxide ion should provide with the form of powder or particulate.Their hydroxide or mixture also possibly be used.
A kind of initial reactant can provide more than one component, AM (XY
4) Z, be the typical case in the above tabulation; Multiple embodiment of the present invention shows, the chemical combination between the initial reactant, such as, alkali metal and halogen, metal and phosphate chemical combination; Therefore, Li, Na, or the fluoride of K can with the phosphoric acid vanadium; Chromium phosphate, perhaps metallic compound (metal phosphate and metal hydroxides) reaction is embodied on the other hand; Initial reactant contains alkali metal, metal and phosphate, and initial reactant can be selected alkali metal A flexibly according to practicality; Metal M,, phosphate (perhaps other XY
4A part), halide/hydroxide Z; Initial reaction
Nonpolar mono-fluor phosphate comprises Na
2PO
3F, K
2PO
3F, (NH
4)
2PO
3F.H
2O, LiNaPO
3F.H
2O, LiKPO
3F, LiNH
4PO
3F,, NaNH
4PO
3F, NaK
3(PO
3F)
2And CaPO
3F.2H
2O; Typical nonpolar mono-fluor phosphate has (NH
4)
2PO
2F
2, NaPO
2F
2, KPO
2F
2, Al (PO
2F
2)
3, Fe (PO
2F
2)
3
In active material, partly or entirely replace phosphorus, just can utilize various silicate and other siliceous compound with silicon; Therefore, among the present invention in the active material useful silicon source comprise orthosilicate, mesosilicate, the ring silicate anion is like, (Si
3O
9)
6-, (Si
6O
18)
12-And homologue and [(SiO
3)
2-]
n, as, LiAl (SiO
3)
2Si or LiAl (SiO
3)
2SiO
2Also can use.
The typical arsenate compound that is used for preparing active material of the present invention comprises H
3AsO
4With contain [H
2AsO
4] and HAsO
4]
2-Anionic salt; The metaantimmonic acid root origin is in tin-containing material Sb in the active material
2O
5, M
ISbO
3(M wherein
IBe to have+metal of 1 valency oxidation state), M
IIISbO
4(M wherein
IIIBe to have+metal of 3 valency oxidation state), M
IISb
2O
7(M wherein
IIBe to have+metal of divalent oxidation state); Other metaantimmonic acid root origins comprise compound L i
3SbO
4, NH
4H
2SbO
4With comprise [SbO
4]
3-Other alkali metal or the salt-mixture of ammonium.
The source that partly or entirely replaces the sulphate cpd of phosphorus with sulphur in the active material comprises that alkali metal and transition metal sulfate and hydrosulphuric acid salt or hybrid metal sulfate mixture are like (NH
4)
2Fe (SO
4)
2, NH
4Fe (SO
4)
2Or the like; At last, germanium contains compound GeO
2Germanium also can be used to partly or entirely replace the phosphorus in the active material.
Preparation contains the active material of modified phosphate group, selects the stoichiometry of the stoichiometry of initial reactant based on the modification group of final products, initial reaction is put together react according to above preparation procedure about phosphate material then; Certainly, partly or completely replace the stoichiometry that phosphate radical need recomputate initial reactant in order to last any modification or replacement phosphate foundation group.
Through heating certain hour, the various A that provide, M and alternative phosphate radical (or other XY in sufficiently high temperature
4) and the compound of Z, carry out solid-state reaction with carbon that is used to react or organic material, initial feed is powder or particle shape preferably, and the mixing of powder can be through various means of different, such as ball milling, such as in mortar and mortar, mixing etc.; Subsequently, this mixture can be pressed into the ball shape, perhaps through passing through adhesive bond together; Form fully bonding mixture, this mixture heats in stove, normally 400 ℃ or higher; Know the formation product, if but reactant Z is a hydroxide, heating-up temperature should be hanged down a bit; Help hydroxyl to enter into product, to avoid the water evaporation; Below provide example.
If contain hydroxyl in the initial reactant, in order to be incorporated into product, that reaction temperature should be lower than 400 ℃, best 250 ℃ or lower; Such as adopting the hydro thermal method reaction can reach this temperature, in hydro-thermal reaction, initial reactant and small amount of liquid such as water, mix, and place pressure reaction still.
This reaction can be non-redox reaction.Under this situation; The metal in the product or the valence state of hybrid metal are identical with original material; Preferably have elemental carbon or organic material to participate in reaction, because carbon granule can be well dispersed in the product, thereby this helps forming the tiny product of particle and improves electrical conductance.
This reaction also can be a reduction reaction, and at least a metal is reduced when heating.In reactant, need reducing agent this moment, and the accessory substance that this reducing agent produces can the use of interfering material in electrode or battery.
This reducing agent can be the form of reduction carbon, and elemental carbon is mixed with other graininess original material.In the reducing metal, carbon is oxidized to carbon monoxide or carbon dioxide.
Metallic compound and carbon mix in the original material, and carbon is wanted enough reducing metals.In order to promote product quality, need suitably excessive initial reactant.Excessive carbon remains in after reaction in the product, can become the conductive agent in the electrode; Because residual carbon is very evenly and fully to be dispersed in the product, therefore help very much conduction, corresponding; Use excessive carbon in process of production; Make it to be well-dispersed in presoma and the product subsequently, the existence of carbon granule can be provided as nuclear location for the generation of product crystal in the initial reactant, and product is made up of granule and crystal grain; Tiny particle agglomeration together, this also helps improving conductivity.
Use organic material separately, perhaps organic material and carbon use simultaneously, also can reach the reduction purpose.Organic material comprises carbon and hydrogen, and it can form catabolite usually such as carbonaceous material when heating; Some representational decomposable processes comprise carbonization, coking, destructive distillation etc.The reducing agent of carbothermic reduction reaction when like this, catabolite can become heating.
The preparation of presoma can also comprise anion, in preparation, the metal in the original material not only with reduction carbon reaction, also with comprise other anionic material reaction, suitable anion comprises XY
4, such as phosphate radical, silicate, sulfate radical, selenate radical or the like.Illustrate, in to the transition metal reduction, react with the material that comprises phosphate radical again, can obtain the phosphate of this transition metal.
M
2O
5, (NH
4)
2HPO
4, MPO
4, M represents at least a metal.Lift an example, M comprises vanadium, and phosphate radical can have phosphate, hydrophosphate, and dihydric phosphate and phosphoric acid etc. provides, and the cation that combines with phosphate anion preferably can produce (such as the ammonia or the water) of volatile product when reaction.
Compound-material of the present invention possibly be by metal precursor compound and the active material that contains other groups, in subsequent reaction, synthesizes; Subsequent reaction possibly comprise reduction reaction further.Carbon reduction reaction possibly be the first step in reaction, and second step or carry out subsequently, the transition metal that contains original chemical forms final active material with other original materials reactions; Contain the transition metal and the synthetic alkali metal compound that contains transition metal of alkali metal compound reaction of presoma, this material is applied to battery active material.
The persursor material and the transition metal in the original material that contain alkali metal compound are not necessarily reacting subsequently simultaneously; The carbon thermal reduction metal oxide reacts like reduction carbon and alkali metal, and the reducing condition in the reaction is provided, as, the lithium molybdenum compound can be according to reaction equation Li
2CO
3+ MoO
2+ [C] → LiMoO
2Produce through reduction reaction, or according to reaction equation Li
2CO
3+ MoO
2→ Li
4Mo
3O
8Produce, in first reaction, molybdenum is reduced into 3 valencys from 4 valencys, and in second reaction, the valence state of molybdenum does not change.
Alkali metal is attached in the reaction of transistion metal compound, possibly have reduction reaction.As in patent 10/045,685 (Nov.7,2001), 09/969,440 (Oct.2,2001) all are described among people's such as 09/974,311 (Oct.9,2001) and Barker the publication WO/01/53198.According to reaction 1/2Li
2CO
3+ M (PO
4)
2+ (NH
4)
3PO
4→ 3LiMPO
4, reduction reaction does not take place when alkali metal and phosphate reaction, wherein M representative+2 metals or metal mixture are like Fe, Co, and Ni.
According to reaction equation 1/2Li
2CO
3+ MPO
4+ [C] → LiMPO
4, reduction reaction has taken place in the reaction, M from+3 be reduced into+2.Saved the volatile matter in the reaction in the formula.
Reduction reaction possibly not take place in the synthetic metallic compound of alkali metal and anion like LiF+MPO
4→ LiMPO
4Reduction reaction also possibly take place like 1/2Li in F
2CO
3+ LiF+MPO
4+ [C] → LiMPO
4F.
Above-mentioned reaction has illustrative.Other carbothermic methods through synthetic metallic compound of alkali metal or transistion metal compound are obviously similar with above-mentioned description; Method of reducing provided by the invention has been used the reduction carbon that reduction carbon maybe can provide reducing atmosphere; Reduction carbon possibly be DIC, and catabolite can be used as the organic carbon of reducing agent, or both combination products.
Before the reaction, raw material are mixed earlier, and raw material should exist with the form of particulate, become a kind of mixed uniformly presoma after the mixing; On the one hand, precursor powder has adopted dry pigmentation, like ball mill, is pressed into coccoidly then, and on the other hand, precursor powder has adopted adhesive when mixing; Selected binding agent can not suppress the reaction between powder particle, and its decomposition or volatilization temperature should be lower than reaction temperature; Before the reaction beginning, binding agent such as mineral oil, glycerine or polymer have volatilized or decomposition becomes the carbon slag with carbonization, in the time of many binding agent fixed solid particulates, also play a part the carbon matrix precursor compound; On the other hand, through using volatile solvent, precursor powder is mixed into wet mixture, be pressed into then spherical, to increase intergranular contact area.
Under a certain temperature, form inorganic transistion metal compound product behind the raw-material mixture heating certain hour.If contain alkali metal in the raw material, reactor product is exactly a kind of alkali metal transistion metal compound so.If contain reducing agent in the raw material, in transistion metal compound, the oxidation valence state of at least a transition metal is lower than the oxidation valence state in the raw material so.
The temperature that the original material particle is heated to should be lower than raw-material melting temperature.In the reaction, at least a portion raw material should remain on solid state.
All can produce CO or CO in the differential responses
2Waste gas.Temperature is high more, helps generating CO more.Some are reflected at when being higher than 600 ℃, carry out more easily, and the optimum temperature range of many reactions is 700～950 ℃ or 700～800 ℃.
In general, can produce CO under the lower temperature
2, higher reaction temperature can produce CO and more residual carbon.Because C generates CO
2Reduction bigger than the reduction that C generates CO; Generate in the reaction of CO2 at C, C becomes 4 valencys from 0 valency, generates in the reaction of CO at C, and C becomes divalent from 0 valency; Here said higher temperature is meant 600～1000 ℃ of scopes, and lower temperature is greatly about 600 ℃.
On the one hand, the present invention utilizes the reproducibility of carbon to prepare target product with a kind of controlled method of uniqueness, and this product has structure and the alkali metal content that is applicable to electrode active material; On the other hand, the present invention also makes and contains Li, metal, and the preparation process economyization of the product of oxygen is oversimplified.Above advantage is in part because reducing agent (carbon) has a kind of formation free energy of oxide to reduce along with the rising of temperature, and the oxide of this carbon is at high temperature stable down than low temperature.This specific character is used for preparing the product with one or more metal ions, the oxidation state of reduction precursor oxidation.This method is utilized a certain amount of carbon, time, a kind of new product of effective combined preparation of temperature and with this product of a kind of new method preparation.
When 700 ℃ of left and right sides, carbon might be transformed into CO, also possibly be transformed into CO
2When temperature during near 600 ℃, C becomes CO
2The reaction of carbon dioxide is main reaction.And when temperature during near 800 ℃, the reaction that C becomes the CO carbon monoxide is main reaction; Because C becomes CO
2The reaction reduction effect of carbon dioxide is stronger, thereby reduces the required carbon of the metal of an atomic unit just still less.Change in the reaction of carbon monoxide at carbon, the carbon of per unit atom is oxidized to+divalent from zeroth order; With this, a unit metal ion (M) of a valence state of reduction only needs the carbon of half atomic unit.Change in the reaction of carbon dioxide at carbon, a unit metal ion (M) of a valence state of reduction is pressed the carbon that stoichiometry only needs 1/4th atomic units, because carbon has become+4 valencys from zeroth order.These relations are applicable to the similar metal and the reaction that needs to reduce per unit oxidation valency that needs reduction.
Initial reactant maybe be by the heating rate heating with 10 ℃ of per minutes; Higher or lower rate selection depends on firing equipment, and transformation and other factors that hope obtains also can be put into the stove with preheating with initial reactant; In case reach the goal response temperature; Reactant (initial reactant) is incubated carry out of a period of time to guarantee to react under reaction temperature, heating suits in non-oxide or inert atmosphere such as argon gas or vacuum, perhaps to have in the reducing atmosphere.
Though can use, reducing atmosphere is optional, after reaction finished, product was suitable to the high temperature cool to room temperature.(just, 10 ℃-40 ℃).Cooldown rate can because more than the relevant heating mentioned factor quantity and difference also is possible with very high speed cooled product, such as the speed of about 100 ℃ of per minutes.
Reaction can be carried out in oxygen or air, and it is main atmosphere that heating is preferably selected non-oxide.Non-oxide is the generation that main atmosphere avoids interference reduction reaction; Non-oxide is that main atmosphere can be used vacuum; Inert gas such as argon gas; Nitrogen and similar gas though oxidizing gas (oxygen or air) can exist, can not have too high concentration in order to avoid disturb carbothermic reduction reaction or this reduction reaction product quality.Thereby existence that it is generally acknowledged any oxidizing gas all is inclined to and the utilance of participating in the carbon of reaction in reduction carbon reaction reduction.In a way, this possibility can be reckoned with, in initial reactant, adds excessive reduction carbon then; But, carbothermic reduction reaction is preferably in practice carries out in the atmosphere of having only small amounts gas to exist.
Reaction also can be carried out in the atmosphere of reducing gas.Nonpolar reducing gas comprises hydrogen, methane, ammonia, carbon monoxide; Generally, suitable reducing gas is to surpass stoichiometric hydrogen.This is through above-mentioned heating steps accomplishing in hydrogen atmosphere; Reducing atmosphere can be the pure reducing gas or the mixture of reducing gas and other gas.Nonpolar reducing atmosphere comprises hydrogen, argon hydrogen gaseous mixture, and nitrogen and hydrogen mixture, carbon monoxide, carbon monoxide hydrogen gaseous mixture, the argon-mixed and similar gas of carbon monoxide, reducing gas can surpass stoichiometry.The reducing gas ratio can be pressed onto above atmospheric pressure from 0.01 atmosphere, and this depends on sample size, and as long as the volume of heating chamber and excessive gas are reaction needed.
Carbothermic reduction reaction of the present invention mainly is a solid phase reaction, and the character that forms product like this in the reaction depends on particle size and the particle and the intergranular way of contact.At first, need to prepare the fine powder of initial reactant.Then Powdered or granular initial reactant is processed mixture through tablet forming technique or adhesive.This mixture is more conducive to granular initial reactant and closely contacts; If initial reactant mixes uneven or the bad product that all can cause of intergranular contact is inhomogeneous, yield poorly or quality low.The more reaction of homogeneous has been guaranteed in the use of reducing gas in carbothermic reduction reaction, thereby generates product, high yield or high-quality product more uniformly.
Instance 1:
Like figure, Fig. 2, Fig. 3 and shown in Figure 4, by the synthetic phosphoric acid vanadium lithium Li of vanadium oxide (vanadium is a pentavalent)
3V
2(PO
4)
3(vanadium is a trivalent) carried out ball milling after raw material mix in molar ratio.
1mol V
2O
5Weight 181.88g;
3mol LiH
2PO
4Weight 315.00g;
2mol carbon (28g);
Carbon needs excessive 0～100% usually.
Method:
1. premixed raw material in molar ratio;
2. mixed raw materials is that medium carries out wet ball grinding with water, and subsequent spray is dry;
3. to above-mentioned material granulation;
4. under inert atmosphere (nitrogen, argon gas or vacuum) heats up with 2 ℃/minute speed, at 850 ℃ of above-mentioned materials of heating;
5. 8 hours heating times;
6. lower the temperature with 2 ℃/minute speed;
7. temperature is taken out material after 25 ℃ from heating furnace;
8. under inert atmosphere protection, material is processed powder.
According to circumstances, can repeat above-mentioned 2～7 steps.
Instance 2:
By the synthetic phosphoric acid vanadium lithium Li of vanadium oxide (vanadium is a pentavalent)
3V
2(PO
4)
3(vanadium is a trivalent) carried out ball milling after raw material mix in molar ratio.
1mol V
2O
5Weight 181.88g;
3/2mol Li
2CO
3Weight 110.84g;
3mol (NH
4)
2HPO
4Weight 396.18g;
Be equivalent to the polybutadiene of 2mol carbon (28g);
Carbon usually need be after amount 0～100%.
Method:
1. premixed raw material in molar ratio;
2. mixed raw materials is carried out granulation;
3. under inert atmosphere (nitrogen, argon gas or vacuum) heats up with 2 ℃/minute speed, at 850 ℃ of above-mentioned materials of heating;
4. 8 hours heating times;
5. lower the temperature with 2 ℃/minute speed;
6. temperature is taken out material after 25 ℃ from heating furnace;
7. under inert atmosphere protection, material is processed powder.
According to circumstances, can repeat above-mentioned 2～7 steps.
Instance 3:
Carbon thermal reduction: MoO
3And Li
2CO
3Produce LiMoO
2, reducing agent can be the organic material that carbon maybe can produce carbon of equal value.
0.5mol Li
2CO
3Weight 36.95g;
1mol MoO
3Weight 143.94g;
1.5mol C (or organic material of equal value) 18.00g;
Carbon usually need be after amount 0～100%.
Method:
1. premixed raw material in molar ratio;
2. mixed raw materials is carried out granulation;
3. under nitrogen atmosphere, heat up the above-mentioned material of heating in 600～950 ℃ scope with 1～5 ℃/minute speed;
4. 2～8 hours heating times;
5. lower the temperature with 1～5 ℃/minute speed;
6. temperature is taken out material after 25 ℃ from heating furnace;
7. under inert atmosphere protection, material is processed powder.
According to circumstances, can repeat above-mentioned 2～7 steps.
Instance 4:
Carbon thermal reduction: MoO
3Produce LiMoO with LiOH
2, reducing agent can be an organic material.
1mol LiOH weight 41.96g;
1mol MoO
3Weight 143.94g;
1.5mol C (providing) by 21g organic material polystyrene-poly butadiene;
Carbon usually need be after amount 0～100%.
Method:
1. premixed raw material in molar ratio;
2. mixed raw materials is carried out granulation;
3. under inert atmosphere (nitrogen, argon gas or vacuum) heats up with 1～5 ℃/minute speed, the above-mentioned material of heating in 600～950 ℃ scope;
4. 2～8 hours heating times;
5. lower the temperature with 1～5 ℃/minute speed;
6. temperature is taken out material after 25 ℃ from heating furnace;
7. under inert atmosphere protection, material is processed powder.
According to circumstances, can repeat above-mentioned 2～7 steps.
Instance 5:
Carbon thermal reduction: MoO
3And Li
2CO
3Produce Li
xMoO
2(0＜x＜2), reducing agent can be organic materials.Li for example
0.74MoO
2, Li
0.85MoO
2Deng.
Overall reaction
x/2Li
2CO
3+1.0MoO
3+3x/2[C]→Li.xMoO
2+3x/2CO+-x/2CO
2
X/2mol Li
2CO
3Weight (x/2 multiply by 73.89) g;
1mol MoO3 weight 143.94g;
3x/2mol C (3x/2 multiply by 14) g hydrocarbon is such as coal tar;
Carbon usually need be after amount 0～100%.
Method:
1. premixed raw material in molar ratio;
2. mixed raw materials is carried out granulation;
3. under inert atmosphere (nitrogen, argon gas or vacuum) heats up with 1～5 ℃/minute speed, the above-mentioned material of heating in 600～950 ℃ scope;
4. 2～8 hours heating times;
5. lower the temperature with 1～5 ℃/minute speed;
6. temperature is taken out material after 25 ℃ from heating furnace;
7. under inert atmosphere protection, material is processed powder.
According to circumstances, can repeat above-mentioned 2～7 steps.
Instance 6:
By the ferric orthophosphate synthesizing lithium ferrous phosphate, after mixing in molar ratio, raw material carry out ball milling.
1mol FePO
4(weight 150.82g);
0.5mol Li
2CO
3(weight 36.95g);
1.0mol carbon 12.0g;
Carbon usually need be after amount 0～100%.
Method:
1. premixed raw material in molar ratio;
2. mixed raw materials is carried out ball milling, granulation subsequently;
3. under inert atmosphere (nitrogen, argon gas or vacuum) heats up with 2 ℃/minute speed, the above-mentioned material of heating in 600～850 ℃ scope;
4. 2～10 hours heating times;
5. lower the temperature with 1～5 ℃/minute speed;
6. temperature is taken out material after 25 ℃ from heating furnace;
7. under inert atmosphere protection, material is processed powder;
According to circumstances, can repeat above-mentioned 2～7 steps.
Instance 7:
By the iron oxide synthesizing lithium ferrous phosphate, after mixing in molar ratio, raw material carry out ball milling.
0.5mol Fe
2O
3Weight 79.85g;
0.5mol Li
2CO
3Weight 36.95g;
1mol (NH
4)
2HPO
4Weight 132.06g;
1.0mol carbon weight 12.0g;
Carbon usually need be after amount 0～100%.
Method:
1. premixed raw material in molar ratio;
2. mixed raw materials is carried out ball milling, granulation subsequently;
3. under inert atmosphere (nitrogen, argon gas or vacuum) heats up with 2 ℃/minute speed, the above-mentioned material of heating in 600～850 ℃ scope;
4. 2～10 hours heating times;
5. lower the temperature with 1～5 ℃/minute speed;
6. temperature is taken out material after 25 ℃ from heating furnace;
7. under inert atmosphere protection, material is processed powder.
According to circumstances, can repeat above-mentioned 2～7 steps.
The invention provides a kind of electrode active material that is used for battery; Said " battery " is meant the device that one or more electrochemical cell of being used to produce electric energy is formed; Each electrochemical cell is by anode, and negative electrode and electrolyte are formed; Two or more electrochemical cells can make up perhaps the battery pack that " stacking " becomes to contain a plurality of batteries, its voltage be all battery cell voltages with.
Electrode active material of the present invention can be used as anode, negative electrode or the two poles of the earth.Said " negative electrode " and " anode " refer to respectively in battery discharge procedure, and the electrode of reduction reaction and oxidation reaction takes place.In the time of battery charge, the position opposite of oxidation reaction and reduction reaction.Active material of the present invention preferentially is used for negative electrode.Here " first-selection " and " preferably " two speech refer to the present invention under certain condition, and the embodiment of confirming benefit is provided.Yet under identical or other condition, other embodiment also can be by preferential selection.In addition, one or more preferential embodiments are not meant that other embodiment is useless, and neither have a mind to other is embodied got rid of outside scope of the present invention.
As stated, the invention provides a kind of active material, comprise lithium or other alkali metal, at least a transition metal, the substituted phosphate radical of phosphate radical or halogen or hydroxyl (referring to " electrode active material " here).The kind electrode active material has chemical formula A
aM
b(XY
4)
cZ
d
It is emphasized that: above only is preferred embodiment of the present invention; Be not that the present invention is done any pro forma restriction; Every foundation technical spirit of the present invention all still belongs in the scope of technical scheme of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (10)
1. the method for the synthetic metallic compound of carbothermic method is characterized in that, may further comprise the steps:
(a) preparation of reactant: the mixture that comprises one or more metallic compounds, phosphate ion source, at least a reduction carbon composition;
(b) make reactant is formed mixture;
(c) add hot mixt, synthetic phosphate metal product salt, the amount of reduction carbon should be controlled at and can make a kind of metal pine for becoming oxidation state adding at least, and does not make it be reduced into simple substance fully.
2. the method for the synthetic metallic compound of carbothermic method according to claim 1 is characterized in that the metallic compound in the said step (a) comprises a kind of transistion metal compound.
3. the method for the synthetic metallic compound of carbothermic method according to claim 1 is characterized in that the metallic compound in the said step (a) comprises the compound of tin.
4. the method for the synthetic metallic compound of carbothermic method according to claim 1 is characterized in that the reduction carbon in the said step (a) comprises DIC.
5. the method for the synthetic metallic compound of carbothermic method according to claim 1 is characterized in that the reduction carbon in the said step (a) comprises organic carbon.
6. the method for the synthetic metallic compound of carbothermic method according to claim 5 is characterized in that, said organic carbon is pined for decomposing adding, and some form with reducing agent in reaction exists.
7. the method for the synthetic metallic compound of carbothermic method according to claim 1 is characterized in that, contains carbohydrate and sucrose in the reduction carbon carbon source in the said step (a).
8. the method for the synthetic metallic compound of carbothermic method according to claim 1 is characterized in that the compound in the said step (a) is to contain a kind of lithium compound.
9. the method for the synthetic metallic compound of carbothermic method according to claim 1 is characterized in that the heating-up temperature in the said step (c) is between 400 ℃ to 1200 ℃.
10. the method for the synthetic metallic compound of carbothermic method according to claim 1 is characterized in that, contains transition metal oxide and phosphate transition metal oxide in the product in the said step (c).
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Cited By (2)
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|---|---|---|---|---|
| CN110137480A (en) * | 2019-06-08 | 2019-08-16 | 桂林理工大学 | Kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon composite preparation method |
| CN110997562A (en) * | 2017-06-16 | 2020-04-10 | 罗地亚经营管理公司 | Process for the preparation of vanadium phosphate |
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| CN1652999A (en) * | 2002-05-17 | 2005-08-10 | 威伦斯技术公司 | Synthesis of metal compounds useful as cathode active materials |
| US20050196334A1 (en) * | 2004-03-04 | 2005-09-08 | Saidi M. Y. | Synthesis of metal phosphates |
| US7101521B2 (en) * | 2000-09-29 | 2006-09-05 | Sony Corporation | Method for the preparation of cathode active material and method for the preparation of non-aqueous electrolyte |
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| US7101521B2 (en) * | 2000-09-29 | 2006-09-05 | Sony Corporation | Method for the preparation of cathode active material and method for the preparation of non-aqueous electrolyte |
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| CN110997562A (en) * | 2017-06-16 | 2020-04-10 | 罗地亚经营管理公司 | Process for the preparation of vanadium phosphate |
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