CN101641814A - Method for producing positive electrode material for secondary battery - Google Patents
Method for producing positive electrode material for secondary battery Download PDFInfo
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- CN101641814A CN101641814A CN200880009680A CN200880009680A CN101641814A CN 101641814 A CN101641814 A CN 101641814A CN 200880009680 A CN200880009680 A CN 200880009680A CN 200880009680 A CN200880009680 A CN 200880009680A CN 101641814 A CN101641814 A CN 101641814A
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Abstract
Disclosed is a positive electrode material for secondary batteries, which is characterized by being composed of a lithium transition metal silicate obtained by firing a mixture of a transition metal compound containing at least one transition metal selected from the group consisting of Mn, Fe, Co and Ni, a lithium compound and a silicon polymer compound. The lithium transition metal silicate can be produced at low cost, while having high lithium absorption/desorption efficiency per unit amount of the transition metal, high stability and high safety. Consequently, the lithium transition metal silicate enables to obtain a secondary battery having excellent charge/discharge characteristics.
Description
Technical field
[0001] the application based on March 27th, 2007 spy in Japanese publication be willing to 2007-82102 number and on December 5th, 2007 spy in Japanese publication be willing to that advocate priority, its content is introduced the application 2007-315091 number.
[0002] the present invention relates to reversibly occlusion and discharge the method for making and the utilization of this positive electrode in secondary cell of the positive electrode of lithium ion.
Background technology
[0003] as secondary cell, used plumbous secondary cell, NI-G secondary cell, Ni-MH battery etc. in the past, but in recent years, the high performance of electronic equipments such as mobile phone, video camera, notebook computer is surprising, therefore, it is also strong day by day to the requirement of high performance to constitute the secondary cell of power supply of these electronic equipments.
[0004] use carbon class material as negative material and use the lithium rechargeable battery of lithium compound as the rechargeable nonaqueous electrolytic battery of positive electrode, by occlusion and the release that utilizes lithium, can suppress the growth of skeleton and the powdered of lithium, therefore, has good cycle life performance, in addition, can also reach high-energy-densityization, high capacity.As above-mentioned lithium compound, for example, LiCoO
2, LiNiO
2, LiMn
2O
4Deng lithium transition-metal oxide practicability.
[0005] still, lithium rechargeable battery uses the formation element of the transition metal of high price as positive electrode, and, most with LiCoO
2, LiNiO
2, LiMn
2O
4Be the positive electrode in the past of representative, each transition metal atoms reversibly occlusion/release lithium atom seldom, be about 0.5.Therefore, hope can more effectively utilize transition metal, and develops with the positive electrode of abundanter and more cheap element as matrix.
[0006] in addition, positive electrode in the past is existing problems aspect stability of working and fail safe generally, specifically, not only can not demonstrate enough stability at aspects such as high-temperature cycle, preservation characteristics, self-discharge characteristics, and owing to decomposes produces oxygen, become main cause on fire, thereby produce the problem of secure context.Can think that its reason is that not only because high voltage has caused the reactivity of interior electrolyte of lithium rechargeable battery and electrode to improve, and the crystalline texture of electrode material itself also is a reason.
[0007] therefore, a part of transition metal of studying at present by substituting in the above-mentioned lithium transition-metal oxide with nonmetalloids such as phosphorus, silicon, boron further improves the characteristic of lithium transition-metal oxide as positive pole.For example, the spy opens the 2001-180939 communique, international disclose No. 2005/99022 brochure and internationally disclose No. 2005/99023 brochure and disclose and pass through LiMn
2O
4, LiCoO
2Be replaced by the technology that phosphorus, silicon, boron wait the high-temperature cycle of improving secondary cell, preservation characteristics, self-discharge characteristics etc. Deng about 10～20% of transition metal.
[0008] yet, in the case, for example, for LiCoO
2; according to reports; silicone content is single phase 10% when following; and reach phase (the SolidState Ionics (2006) that will form other at 35% o'clock; 177 (3-4); 317-322), replace transition metal and the system that forms, the material that to can be described as a kind of mol ratio that obviously is different from transition metal and silicic acid be about 1: 1 lithium transition-metal silicate with a spot of silicon.
[0009] on the other hand, about the mol ratio of transition metal and silicic acid about 1: 1 lithium transition-metal silicate, for example have with the report (Electrochemistry Communications 7 (2005) 156-160s) of lithium metasilicate as the lithium transition-metal silicate in silicon source, this silicate demonstrates can be as the possibility of the positive pole of so-called lithium rechargeable battery.
[0010] yet, the mol ratio of transition metal and silicic acid is about 1: 1 a lithium transition-metal silicate, owing to generally synthesize by carrying out high temperature sintering as raw material with inorganic compounds such as inorganic lithium salt, transition metal salt, silicon dioxide, be difficult to control degree of crystallinity, particle diameter and the particle size distribution of product, therefore, its performance is compared with lithium transition-metal oxide in the past, may not be suitable for positive electrode.That is, there is following problem substantially in these materials: reversibly the capacity of occlusion and release lithium ion is very low, and, along with discharging and recharging operation repeatedly, the charge-discharge characteristic deterioration.
Patent documentation 1: the spy opens the 2001-180939 communique
Patent documentation 2: the international brochure that discloses No. 2005/99022
Patent documentation 3: the international brochure that discloses No. 2005/99023
Non-patent literature 1:Solid State Ionics (2006), 177 (3-4), 317-322
Non-patent literature 2:Electrochemistry Communications 7 (2005) 156-160
Summary of the invention
The problem that invention will solve
[0011] the present invention carries out in view of the present situation of above-mentioned conventional art just, the objective of the invention is to, and a kind of secondary cell is provided, and it has following characteristic: the occlusion and the release efficiency height of the lithium of (1) per unit amount transition metal; (2) cost is low; (3) stability and safe; And (4) has good charge-discharge characteristic.
Be used to solve the means of problem
[0012] above-mentioned purpose realizes by following operation, when manufacturing contains formula:
[changing 1] Li
aM
bSi
cO
4
(in the formula,
M is at least a kind of transition metal that is selected among Mn, Fe, Co and the Ni, and a, b and c are for satisfying the number of 1＜a≤3,0.5≤b≤1.5,0.5≤c≤1.5)
During the positive electrode material for secondary battery of lithium transition-metal silicate of expression, will contain at least:
(A) be selected from least a kind of transition metal among Mn, Fe, Co and the Ni and/or contain this transition metal transistion metal compound,
(B) lithium compound and
(C) silicon family macromolecule compound
Mixture sintering, obtain above-mentioned lithium transition-metal silicate.
[0013] above-mentioned sintering temperature is preferably below 900 ℃.The lithium transition-metal silicate that obtains is preferably the particle of average primary particle diameter less than 500nm.
[0014] and then, (A) compound that contains transition metal in the composition is preferably at least a kind of transistion metal compound selecting the carbonyl-complexes of the halide of sulfate, transition metal of nitrate, the transition metal of carbonate, the transition metal of oacetic acid salt, the transition metal of acetylacetonate, the transition metal of carboxylate, the transition metal of alkoxide, the transition metal of hydroxide, the transition metal of oxide from transition metal, transition metal and transition metal.
[0015] in addition, (B) lithium compound of composition is preferably at least a kind of lithium compound selecting the sulfate of nitrate, lithium of carbonate, the lithium of oacetic acid salt, the lithium of acetylacetonate, the lithium of carboxylate, the lithium of alkoxide, the lithium of hydroxide, the lithium of oxide from lithium, lithium and the lithium halide.
[0016] (C) the silicon family macromolecule compound of composition is preferably at least a kind of silicon family macromolecule compound selecting from polysilane, polysilazane, polysiloxanes, Polycarbosilane and their mixture, is preferably especially by repetitive:
[changing 2] C
6H
5SiO
1.5
The polyphenylene silsesquioxane of expression.
[0017] contains the anode of secondary cell that adopts the positive electrode material for secondary battery that above-mentioned manufacture method makes, be applicable to the component parts of secondary cell.
The invention effect
[0018], can adopt that simple manufacturing process synthesizes that average grain diameter is little, narrow particle size distribution, have lithium transition-metal silicate particles as the premium properties of secondary battery positive electrode material according to the present invention.
[0019] in addition, by with this lithium transition-metal silicate particles as positive electrode, can provide occlusion and the release efficiency height of a kind of per unit amount transition metal, cost is low, stable and safe and have a secondary cell of good charge-discharge characteristic to lithium.Especially, the stability of secondary cell of the present invention under hot conditions increases substantially.
Description of drawings
[0020] X-ray diffractogram of [Fig. 1] comparative example 1
The X-ray diffractogram of [Fig. 2] embodiment 1
The electron micrograph (Fig. 3 (b)) of electron micrograph of [Fig. 3] comparative example 1 (Fig. 3 (a)) and embodiment 1
[Fig. 4] illustrates the figure of the flash-over characteristic of comparative example 1 (dotted line) and embodiment 1 (solid line)
The X-ray diffractogram of [Fig. 5] comparative example 2 (a) and embodiment 2 (b)
The electron micrograph (Fig. 6 (b)) of electron micrograph of [Fig. 6] comparative example 2 (Fig. 6 (a)) and embodiment 2
[Fig. 7] illustrates the figure of the flash-over characteristic of comparative example 2 ((a) figure) and embodiment 2 ((b) figure)
The X-ray diffractogram of [Fig. 8] comparative example 3
The X-ray diffractogram of [Fig. 9] embodiment 3
The electron micrograph of [Figure 10] comparative example 3
The electron micrograph of [Figure 11] embodiment 3
[Figure 12] illustrates the figure of the flash-over characteristic of comparative example 3
[Figure 13] illustrates the figure of the flash-over characteristic of embodiment 3
[Figure 14] illustrates the figure of the flash-over characteristic of embodiment 4
Embodiment
[0021] manufacture method of positive electrode material for secondary battery of the present invention, it is characterized in that, with silicon family macromolecule compound as the silicon supply source, the silicon family macromolecule compound that will be somebody's turn to do (C) composition and (B) lithium compound and (A) transition metal and/or transistion metal compound mix, with this mixture sintering, can obtain primary particle size, particle size distribution, the controlled lithium transition-metal silicate of system of crystallization thus.The positive electrode that contains the lithium transition-metal silicate that obtains according to manufacture method of the present invention can be with reversibly occlusion and discharge lithium of high efficiency, and its stability and fail safe are good.
The silicon family macromolecule compound of (C) composition that [0022] uses among the present invention, so long as contain the oligomer or the polymer of silicon, its kind is just unqualified.As above-mentioned silicon family macromolecule compound, for example can enumerate, contain to have polysilane that silicon-silicon bond is the construction unit of feature, to contain to have polysilazane that silicon-nitrogen-silicon key is the construction unit of feature, to contain to have polysiloxanes that silicon-oxygen-silicon bound is the construction unit of feature, to contain to have the Polycarbosilane of construction unit that silico-carbo-silicon key is a feature and their mixture.
[0023], can use the polysilane of for example representing by averaging unit chemical formula (I) as polysilane:
[changing 3] (R
1R
2R
3Si)
d(R
3R
4Si)
e(R
5Si)
f(Si)
g(I)
(in the formula,
R
1～R
5Replacement or unsubstituted alkyl, alkoxyl or the halogen atom of representing 1 valency of hydrogen atom, carbon number 1～20 independently of one another;
D, e, f, g represent 0 or positive number.But, d+e+f+g=1).
[0024] polysilane of above-mentioned averaging unit chemical formula (I) expression is by (R
1R
2R
3Si), (R
3R
4Si), (R
5Si) and (Si) at least 1 unit in the construction unit of expression constitutes, and particularly, for example can enumerate, and contains (R
1R
2R
3Si) and (R
3R
4Si) linear polysilanes of unit; Contain (R
3R
4Si) cyclic polysilanes of unit; Contain (R
5Si) or (Si) branched polysilane of unit (polysilyne); Contain (R
1R
2R
3Si) and (R
5Si) polysilane of unit; Contain (R
1R
2R
3Si) and (Si) polysilane of unit; Contain (R
5Si) and (Si) polysilane of unit; Contain (R
3R
4Si) and (R
5Si) polysilane of unit; Contain (R
3R
4Si) and (Si) polysilane of unit; Contain (R
1R
2R
3Si), (R
3R
4Si) and (R
5Si) polysilane of unit; Contain (R
1R
2R
3Si), (R
3R
4Si) and (Si) polysilane of unit; Contain (R
1R
2R
3Si), (R
5Si) and (Si) polysilane of unit; Contain (R
3R
4Si), (R
5Si) and (Si) polysilane of unit; Contain (R
1R
2R
3Si), (R
3R
4Si), (R
5Si) and (Si) polysilane of unit etc.By (R
1R
2R
3Si), (R
3R
4Si), (R
5Si) and (Si) the preferred number of repeat unit of the construction unit of expression respectively does for oneself 2～10000, and more preferably 3～1000, more preferably 3～500.
[0025], is preferably the monovalence alkyl that is selected from alkyl, thiazolinyl, aralkyl and the aryl as above-mentioned alkyl.
[0026] as alkyl, preferred C
1～C
12Alkyl, more preferably C
1～C
6Alkyl.Alkyl is preferably straight or branched alkyl, cycloalkyl or the cycloalkylidene (alkylidene of straight or branched (C such as preferred methylene, ethylidene
1～C
6Alkylidene) with carbocyclic ring (preferred C
3～C
8Ring) any the alkyl that is combined to form).
[0027] as the straight or branched alkyl, preferred straight or branched C
1～C
6Alkyl for example can be enumerated, methyl, ethyl, n-pro-pyl, isopropyl, butyl, the tert-butyl group, amyl group, hexyl etc., special preferable methyl.
[0028] as cycloalkyl, preferred C
4～C
6Alkyl for example can be enumerated, cyclobutyl, cyclopenta, cyclohexyl etc., preferred cyclopenta and cyclohexyl.
[0029] as thiazolinyl, preferred C
2～C
12Thiazolinyl, more preferably C
2～C
6Thiazolinyl.As C
2～C
6Thiazolinyl can be enumerated vinyl, acrylic, cyclobutenyl, pentenyl, hexenyl etc., special preferred vinyl.
[0030] as aralkyl, preferred C
7～C
12Aralkyl.As C
7～C
12Aralkyl can be enumerated benzyl, phenethyl, phenyl propyl etc.
[0031] as aryl, preferred C
6～C
12Aryl can be enumerated phenyl, naphthyl, tolyl.
[0032] above-mentioned alkyl can have substituting group, as this substituting group, can enumerate halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom; Hydroxyl; C such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy
1～C
6Alkoxyl; Amino; Amide groups; Nitro; Epoxy radicals etc.Substituting group can be bonded on the optional position in hydrocarbon chain, saturated or unsaturated ring and the aromatic rings.
[0033] in addition, as R
1～R
5Alkoxyl, can enumerate for example methoxyl group, ethyoxyl, positive propoxy, isopropoxy.
[0034] in addition, as R
1～R
5Halogen atom, can enumerate for example fluorine atom, chlorine atom, bromine atoms, iodine atom.
[0035] above-mentioned polysilane can adopt various known methods to prepare.For example can enumerate, carry out the method (J.Am.Chem.Soc., 110,124 (1988), Macromolecules, 23,3423 (1990) etc.) of the dehalogenation reaction of halogenated silanes (halosilane) class in the presence of alkali-metal; Carry out disilane the method (Macromolecules, 23,4494 (1990) etc.) of anionic polymerization; Utilize the electrode reduction to carry out the method (J.Chem.Soc., Chem.Commun., 1161 (1990), J.Chem.Soc., Chem.Commun., 897 (1992) etc.) of the dehalogenation reaction of halogenated silanes class; In the presence of magnesium, carry out the method (WO98/29476 communique etc.) of the dehalogenation reaction of halogenated silanes class; In the presence of metallic catalyst, carry out the method methods such as (spy open flat 4-334551 communique etc.) of the dehydrogenation reaction of hydrogen silane (hydrosilane) class.
[0036] polysilane also can be the copolymer with other polymer.For example can use, contain the copolymer of polysilane unit and poly-silicon alkylidene (silalkylene) (for example, poly-silicon ethylidene (silethylene)) unit; The copolymer that contains polysilane unit and poly-silicon arlydene (silarylene) (for example, poly-silicon phenylene (silphenylene)) unit; The copolymer that contains polysilane unit and polysilazane unit; The copolymer etc. that contains polysilane unit and polysiloxane unit is as polysilane.
[0037], for example, can use polysilazane by averaging unit chemical formula (II) expression as polysilazane.：
[changing 4] (R
6R
7R
8SiNR
9)
h(R
10R
11SiNR
12)
i(R
13SiNR
14)
j(SiNR
15)
k(II)
(in the formula,
R
6～R
15Replacement or unsubstituted alkyl, alkoxyl or the halogen atom of representing 1 valency of hydrogen atom, carbon number 1～20 independently of one another;
H, i, j, k represent 0 or positive number.But, h+i+j+k=1)
Herein, alkyl is meant and above-mentioned R
1～R
5The identical alkyl of definition.
[0038] polysilazane of above-mentioned averaging unit chemical formula (II) expression is by (R
6R
7R
8SiNR
9), (R
10R
11SiNR
12), (R
13SiNR
14) and (SiNR
15) at least a kind of unit in the construction unit of expression constitutes, and specifically, for example can enumerate, and contains (R
6R
7R
8SiNR
9) and (R
10R
11SiNR
12) the straight chain polysilazane of unit; Contain (R
10R
11SiNR
12) cyclic polysilazane of unit; Contain (R
13SiNR
14) or (SiNR
15) the side chain polysilazane of unit; Contain (R
6R
7R
8SiNR
9) and (R
13SiNR
14) polysilazane of unit; Contain (R
6R
7R
8SiNR
9) and (SiNR
15) polysilazane of unit; Contain (R
13SiNR
14) and (SiNR
15) polysilazane of unit; Contain (R
10R
11SiNR
12) and (R
13SiNR
14) polysilazane of unit; Contain (R
10R
11SiNR
12) and (SiNR
15) polysilazane of unit; Contain (R
6R
7R
8SiNR
9), (R
10R
11SiNR
12) and (R
13SiNR
14) polysilazane of unit; Contain (R
6R
7R
8SiNR
9), (R
10R
11SiNR
12) and (SiNR
15) polysilazane of unit; Contain (R
6R
7R
8SiNR
9), (R
13SiNR
14) and (SiNR
15) polysilazane of unit; Contain (R
10R
11SiNR
12), (R
13SiNR
14) and (SiNR
15) polysilazane of unit; Contain (R
6R
7R
8SiNR
9), (R
10R
11SiNR
12), (R
13SiNR
14) and (SiNR
15) polysilazane etc. of unit.(R
6R
7R
8SiNR
9), (R
10R
11SiNR
12), (R
13SiNR
14) and (SiNR
15) the preferred repeat units number of construction unit of expression, respectively do for oneself 2～10000, more preferably 3～1000, more preferably 3～500.
[0039] polysilazane can adopt method well known in the art to prepare.The preparation method of polysilazane for example is recorded in the United States Patent (USP) No. 4312970, No. 4340619, No. 4395460, No. 4404153, No. 4482689, No. 4397828, No. 4540803, No. 4543344, No. 4835238, No. 4774312, No. 4929742 and No. 4916200.In addition, be also recorded in people such as Burns, J.Mater.Sci., 22 (1987), among the pp 2609-2614.
[0040] polysilazane also can be the copolymer with other polymer.For example can use, contain the copolymer of polysilazane unit and poly-silicon alkylidene (for example, poly-silicon ethylidene) unit; The copolymer that contains polysilazane unit and poly-silicon arlydene (for example, poly-silicon phenylene) unit; Contain polysilazane unit and polysiloxanes (for example ,-(CH
3)
2SiO-) copolymer of unit etc. is as polysilazane.
[0041], for example, can use polysiloxanes by averaging unit chemical formula (III) expression as polysiloxanes:
[changing 5] (R
16R
17R
18SiO
1/2)
1(R
19R
20SiO
2/2)
m(R
21SiO
3/2)
n(SiO
4/2).(III)
(in the formula,
R
16～R
21Replacement or unsubstituted alkyl, alkoxyl or the halogen atom of representing 1 valency of hydrogen atom, carbon number 1～20 independently of one another;
L, m, n, o represent 0 or positive number.But, 1+m+n+o=1)
Herein, alkyl is meant and above-mentioned R
1～R
5The identical alkyl of definition.
[0042] polysiloxanes of above-mentioned averaging unit chemical formula (III) expression is by (R
16R
17R
18SiO
1/2), (R
19R
20SiO
2/2), (R
21SiO
3/2) and (SiO
4/2) at least a kind of unit in the construction unit of expression constitutes, and specifically, for example can enumerate, and contains (R
16R
17R
18SiO
1/2) and (R
19R
20SiO
2/2) the straight chain polysiloxanes of unit; Contain (R
19R
20SiO
2/2) cyclic polysiloxanes of unit; Contain (R
21SiO
3/2) or (SiO
4/2) the side chain polysiloxanes of unit; Contain (R
16R
17R
18SiO
1/2) and (R
21SiO
3/2) polysiloxanes of unit; Contain (R
16R
17R
18SiO
1/2) and (SiO
4/2) polysiloxanes of unit; Contain (R
21SiO
3/2) and (SiO
4/2) polysiloxanes of unit; Contain (R
19R
20SiO
2/2) and (R
21SiO
3/2) polysiloxanes of unit; Contain (R
19R
20SiO
2/2) and (SiO
4/2) polysiloxanes of unit; Contain (R
16R
17R
18SiO
1/2), (R
19R
20SiO
2/2) and (R
21SiO
3/2) polysiloxanes of unit; Contain (R
16R
17R
18SiO
1/2), (R
19R
20SiO
2/2) and (SiO
4/2) polysiloxanes of unit; Contain (R
16R
17R
18SiO
1/2), (R
21SiO
3/2) and (SiO
4/2) polysiloxanes of unit; Contain (R
19R
20SiO
2/2), (R
21SiO
3/2) and (SiO
4/2) polysiloxanes of unit; Contain (R
16R
17R
18SiO
1/2), (R
19R
20SiO
2/2), (R
21SiO
3/2) and (SiO
4/2) polysiloxanes etc. of unit.(R
16R
17R
18SiO
1/2), (R
19R
20SiO
2/2), (R
21SiO
3/2) and (SiO
4/2) the preferred repeat units number of construction unit of expression, respectively do for oneself 2～10000, more preferably 3～1000, more preferably 3～500.
[0043] polysiloxanes can adopt method well known in the art to prepare.The preparation method of polysiloxanes does not have particular determination.The most general method, polysiloxanes can prepare by the hydrolysis of organochlorine for silanes.This method and other method are recorded in Noll, and Chemistry and Technology of Silicones is in the 5th chapter (second edition, German translation, Academic Press, 1968).
[0044] polysiloxanes also can be the copolymer with other polymer.For example can use, contain the copolymer of polysiloxane unit and poly-silicon alkylidene (for example, poly-silicon ethylidene) unit; The copolymer that contains polysiloxane unit and poly-silicon arlydene (for example, poly-silicon phenylene) unit; The copolymer that contains polysiloxane unit and polysilazane unit; The copolymer etc. that contains polysiloxane unit and polysilane unit is as polysiloxanes.
[0045], for example, can use Polycarbosilane by averaging unit chemical formula (IV) expression as Polycarbosilane:
[changing 6] (R
22R
23R
24SiCR
25R
26)
p(R
27R
28SiCR
29R
30)
q(R
31SiCR
32R
33)
r(SiCR
34R
35)
s(IV)
(in the formula,
R
22～R
35Replacement or unsubstituted alkyl, alkoxyl or the halogen atom of representing 1 valency of hydrogen atom, carbon number 1～20 independently of one another;
P, q, r, s represent 0 or positive number.But, p+q+r+s=1)
Herein, alkyl is meant and above-mentioned R
1～R
5The identical alkyl of definition.
[0046] Polycarbosilane of above-mentioned averaging unit chemical formula (IV) expression is by (R
22R
23R
24SiCR
25R
26), (R
27R
28SiCR
29R
30), (R
31SiCR
32R
33) and (SiCR
34R
35) at least a kind of unit in the construction unit of expression constitutes, and specifically, for example can enumerate, and contains (R
22R
23R
24SiCR
25R
26) and (R
27R
28SiCR
29R
30) the straight chain Polycarbosilane of unit; Contain (R
27R
28SiCR
29R
30) the ring-type Polycarbosilane of unit; Contain (R
31SiCR
32R
33) or (SiCR
34R
35) the side chain Polycarbosilane of unit; Contain (R
22R
23R
24SiCR
25R
26) and (R
31SiCR
32R
33) Polycarbosilane of unit; Contain (R
22R
23R
24SiCR
25R
26) and (SiCR
34R
35) Polycarbosilane of unit; Contain (R
31SiCR
32R
33) and (SiCR
34R
35) Polycarbosilane of unit; Contain (R
27R
28SiCR
29R
30) and (R
31SiCR
32R
33) Polycarbosilane of unit; Contain (R
27R
28SiCR
29R
30) and (SiCR
34R
35) Polycarbosilane of unit; Contain (R
22R
23R
24SiCR
25R
26), (R
27R
28SiCR
29R
30) and (R
31SiCR
32R
33) Polycarbosilane of unit; Contain (R
22R
23R
24SiCR
25R
26), (R
27R
28SiCR
29R
30) and (SiCR
34R
35) Polycarbosilane of unit; Contain (R
22R
23R
24SiCR
25R
26), (R
31SiCR
32R
33) and (SiCR
34R
35) Polycarbosilane of unit; Contain (R
27R
28SiCR
29R
30), (R
31SiCR
32R
33) and (SiCR
34R
35) Polycarbosilane of unit; Contain (R
22R
23R
24SiCR
25R
26), (R
27R
28SiCR
29R
30), (R
31SiCR
32R
33) and (SiCR
34R
35) Polycarbosilane etc. of unit.(R
22R
23R
24SiCR
25R
26), (R
27R
28SiCR
29R
30), (R
31SiCR
32R
33) and (SiCR
34R
35) the preferred repeat units number of construction unit of expression, respectively do for oneself 2～10000, more preferably 3～1000, more preferably 3～500.
[0047] Polycarbosilane can adopt method well known in the art to prepare.The preparation method of Polycarbosilane for example is recorded in people such as J.Dunogues., Macromolecules, 21,30 (1988), people such as No. 3293194 specification of United States Patent (USP), N.S.Nametkin, Dokl.Akad.Nauk SSSR, 208,1112 (1973), W.A.Kriner, J.Polym.Sci., Part A-1,4,444 (1966), people such as N.S.Nametkin, Dokl.Akad.Nauk SSSR, 170,1088 (1966), C.S.Cundy, C.Eaborn, M.F.Lappert, J.Organomet.Chem., in 44 (2), 291 (1972).
[0048] Polycarbosilane also can be the copolymer with other polymer.For example can use, contain the copolymer of Polycarbosilane unit and poly-silicon alkylidene (for example, poly-silicon ethylidene) unit; The copolymer that contains Polycarbosilane unit and poly-silicon arlydene (for example, poly-silicon phenylene) unit; Contain Polycarbosilane unit and polysiloxanes (for example ,-(CH
3)
2SiO-) copolymer of unit etc. is as Polycarbosilane.
[0049] shape of polysilane, polysilazane, polysiloxanes and Polycarbosilane does not have particular determination, can be solid, shaped, aqueous, pasty state etc., considers from aspects such as operability, is preferably solid, shaped.
[0050] in these silicon family macromolecule compound, from silicone content can significantly not reduce, have sufficient chemical stability, at normal temperatures low with airborne processing ease, cost of material and manufacturing process cost, have industrial aspects such as advantage such as excellent economy and consider, preferably contain the polysiloxanes of unit with silicon-oxygen-silicon bound.
[0051] in the polysiloxanes, from price, the easiness that obtains, reactive, the easiness aspect of reaction control is considered, as the substituting group on the silicon, special hope is to contain to have hydrogen, methyl, n-pro-pyl, phenyl, methoxyl group, the macromolecule of the construction unit of ethyoxyl, and consider from the problem of polymeric main chain break and the dissipation of thing followed low-molecular-weight molecule, be preferably low poly-(aminomethyl phenyl) siloxanes of volatility with siloxane unit, poly-(diphenyl) siloxanes, poly-(dimethoxy) siloxanes, poly-(diethoxy) siloxanes, the average that especially preferably has silicon is the so-called silicones of the siloxane bond more than 2.
[0052], can enumerate particularly as this silicones
By repetitive: HSiO
1.5Poly-(hydrogen silsesquioxane (hydrogensilsesquioxane)) of expression,
By repetitive: C
6H
5SiO
1.5Poly-(phenyl silsesquioxane) of expression,
By repetitive: CH
3SiO
1.5Poly-(methyl silsesquioxane) of expression,
By repetitive: C
6H
5SiO
1.5The phenyl silsesquioxane and the repetitive of expression: (CH
3)
2The copolymer of the dimethyl siloxane that SiO represents,
By repetitive: CH
3SiO
1.5The methyl silsesquioxane and the repetitive of expression: (CH
3)
2The copolymer of the dimethyl siloxane that SiO represents,
By repetitive: C
6H
5SiO
1.5The phenyl silsesquioxane and the repetitive of expression: n-C
3H
7SiO
1.5The copolymer of the n-pro-pyl silsesquioxane of expression,
By repetitive: (CH
3O)
2Poly-(dimethoxysiloxane) that SiO represents,
By repetitive: (C
2H
5O)
2Poly-(the diethoxy siloxanes) that SiO represents,
By repetitive: CH
3OSiO
1.5Poly-(the methoxyl group silsesquioxane) of expression,
By repetitive: C
2H
5OSiO
1.5Poly-(the ethyoxyl silsesquioxane) of expression.
Preferably by repetitive:
[changing 7] C
6H
5SiO
1.5
The poly-phenyl polysiloxanes such as (phenyl silsesquioxanes) of expression.
[0053] lithium compound of above-mentioned (B) composition as long as contain elemental lithium, does not just have particular determination, for example can use the oxide of lithium; Hydroxide; With methoxide, ethylate is the alkoxide of representative; With acetate, oxalates is the carboxylate of representative; Acetylacetonate; Oacetic acid salt; Carbonate; Nitrate; Sulfate; With lithium chloride, lithium bromide, lithium iodide is the lithium halide of representative.Illustrated,, can be used the above-mentioned lithium compound more than 2 kinds as (B) composition.
[0054] transistion metal compound of above-mentioned (A) composition so long as contain the compound that is selected from least a kind of transition metal in manganese, iron, cobalt and the nickel, does not just have particular determination, for example can use the oxide of above-mentioned transition metal; Hydroxide; With methoxide, ethylate is the alkoxide of representative; With acetate, oxalates is the carboxylate of representative; Acetylacetonate; Oacetic acid salt; Carbonate; Nitrate; Sulfate; With chloride, bromide, iodide is the halide of representative, the carbonyl-complexes of these metals.In addition, when (perhaps in the oxidizing atmosphere) implements manufacture method of the present invention in air atmosphere,, can use transition metal as raw material as (A) composition.In addition, when in inert atmosphere, implementing manufacture method of the present invention, as (A) composition, the particulate that can use transition metal and+3 valencys ,+4 valencys or+mixture of the transistion metal compound of the above state of oxidation of 4 valencys.
[0055] transistion metal compound of above-mentioned (A) composition is selected from manganese, iron, cobalt and nickel, as above-mentioned (A) composition, can use the different metal more than 2 kinds or the transistion metal compound of metal.That is, can use for example by manganese compound and the illustrated 2 kinds of transistion metal compounds of iron compound, manganese compound and cobalt compound, manganese compound and nickel compound, iron compound and cobalt compound, iron compound and nickel compound, cobalt compound and nickel compound; Perhaps use for example by the illustrated 3 kinds of transistion metal compounds of manganese compound, iron compound and nickel compound; Can also use the mixture of manganese, iron, cobalt, these 4 kinds of transistion metal compounds of nickel.The lithium transition-metal silicate anodal material that contains multiple transition metal, per unit transition metal amount can have discharging and recharging of more lithium ion, can expect the improvement of the speed of discharging and recharging, the improvement of lattice stability, the raising of chemical stability.
[0056] among the present invention, by with above-mentioned transistion metal compound, above-mentioned lithium compound and above-mentioned silicon family macromolecule compound,, obtain the lithium transition-metal silicate of representing by following formula with this mixture sintering:
[changing 8] Li
aM
bSi
cO
4
(in the formula,
M is at least a kind of transition metal that is selected among Mn, Fe, Co and the Ni, and a, b and c are for satisfying the number of 1＜a≤3,0.5≤b≤1.5,0.5≤c≤1.5 〉
The scheme that preferred sinter is formed, a, b and c are for satisfying the number of 0＜a≤2.66,0.67≤b≤1.33,0.67≤c≤1.33, and particularly preferred scheme is for satisfying the number of 0＜a≤2.4,0.8≤b≤1.2,0.8≤c≤1.2.In addition, preferred b+c more preferably satisfies the number of 1.5≤b+c≤2.5 for satisfying the number of 1.2≤b+c≤2.8, is preferably the number that satisfies 1.8≤b+c≤2.2 especially.As long as the lithium transition-metal silicate that obtains among the present invention contains at least a kind of transition metal that is selected from cobalt, manganese, iron and the nickel, in addition, can also contain other element such as Cu, Cr, Ti, Mg, Al, Zr, Nb, K, B, P, Ga, Ge, S.As above-mentioned lithium transition-metal silicate, for example can enumerate: Li
2CoSiO
4, Li
2FeSiO
4, Li
2MnSiO
4, Li
2NiSiO
4, Li
2Fe
0.5Mn
0.5SiO
4Deng.In addition, above-mentioned lithium transition-metal silicate also can contain lattice defect in its crystalline texture.
[0057] scheme of above-mentioned mixing is unqualified, for example, can be according to the lithium in the lithium transition-metal silicate of target, transition metal and silicic acid three's mol ratio, pulverize with ball mill etc. and mix while will contain the above-mentioned lithium compound of lithium, transition metal and the silicon suitable, above-mentioned transition metal and/or transistion metal compound and above-mentioned silicon family macromolecule compound with this mol ratio.In addition, when carrying out above-mentioned pulverizing and mix, preferably add organic solvents such as acetone, alcohols.Illustrated, when use straight chain polysiloxanes and so on because volatilizations etc. are former thereby might lose those raw materials of a part of raw material the time, by using the raw material of excess quantity, the composition that can prevent the sinter that the obtains composition that departs from objectives.
[0058] scheme of above-mentioned sintering is also unqualified, for example, can according to the lithium transition-metal silicate of target under sintering condition oxidation-reduction stability and the state of oxidation of raw material suit to select sintering atmosphere.For example, when obtaining oxidation-stabilized lithium transition-metal silicate (Li
2CoSiO
4Deng) time, can in air atmosphere, (perhaps in the oxidizing atmosphere) carry out sintering, when obtaining the unsettled lithium transition-metal silicate of oxidation (Li
2FeSiO
4Deng) time, be to carry out sintering in the nonoxidizing atmosphere of representative or the inert atmosphere that contains reducibility gas such as hydrogen, carbon monoxide preferably with argon, nitrogen.
[0059] above-mentioned sintering temperature does not have particular determination, preferably below 900 ℃, particularly preferably in 500 ℃～900 ℃, more preferably 500～800 ℃, is preferably especially in 500～700 ℃ the temperature range.This is because if under the temperature more than the upper limit of above-mentioned scope, the crystallization meeting of the lithium transition-metal silicate that then obtains grows into big particle, and is therefore not preferred; If less than the lower limit of above-mentioned scope, then be difficult to generate lithium transition-metal silicate.
[0060] the lithium transition-metal silicate that obtains like this, be that average grain diameter is little, narrow particle size distribution microgranular, have premium properties as the positive electrode of secondary cell.The average primary particle diameter of lithium transition-metal silicate is more preferably less than 300nm preferably less than 500nm, further preferably less than 200nm, especially preferably less than 100nm.
[0061] the lithium transition-metal silicate particulate that obtains according to manufacture method of the present invention can adopt method commonly used in the art, makes the positive pole that secondary cell is used.For example, by conductive agent such as above-mentioned lithium transition-metal silicate and carbon black, acetylene black and poly-binding agents such as (vinylidenes) are mixed, and load on the positive electrode collector that constitutes by metal forming etc. and make positive pole.Illustrated, as required, when above-mentioned mixing, also can be added organic solvents such as dimethyl formamide.
[0062] positive pole of the present invention, with respect to per unit transition metal, can be with the reversibly occlusion and discharge lithium of high relatively efficient, and also stability and fail safe are good.In addition, constitute the aboundresources of the formation element of anodal lithium transition-metal silicate, manufacture method is simple, therefore, can reduce anodal manufacturing cost.
[0063] secondary cell of the present invention possess above-mentioned positive pole, by occlusion reversibly with discharge negative pole and the nonaqueous electrolyte that the negative material of lithium constitutes.
[0064] as long as the reversibly occlusion and release lithium of the raw material of above-mentioned negative material is just unqualified, big carbonaceous material, oxide material or the alloy material of preferred lithium capacity (but doping of lithium).
[0065], can use thermally decomposed carbon class, coke class (pitch coke, needle coke, petroleum coke etc.), graphite-like, vitreous carbon class, organic macromolecule sinter (phenolic resins, furane resins etc. are formed in suitable sintering temperature, carbonization), carbon fiber, active carbon etc. as above-mentioned carbonaceous material.
[0066] as above-mentioned oxide material, can use in metal oxide or the nonmetal oxide any, can enumerate for example oxide of titanium, vanadium, silicon.Above-mentioned metal oxide or above-mentioned nonmetal oxide can also contain carbon.
[0067] above-mentioned alloy material is the compound of following chemical formulation:
[changing 9] M '
tM "
uLi
v
(in the formula,
The element more than a kind of M ' expression can formation alloy with lithium;
M " the element a kind or more of expression except lithium and M ';
T represents positive number, and u represents 0 or positive number, v represent 0 or positive number).
[0068] as M ', preferred 2A, 3A, 4A, 5A, 6A, 1B, 2B, 3B, 4B or 5B family element, more preferably 4B family element, further preferred Si or Sn, preferred especially Si.
[0069] as M ", preferred M ' 2A, 3B, 4B, 5B or 6B family element, more preferably semiconductor element such as B, Si, As in addition.
[0070] as above-mentioned alloy material, for example can enumerate: the simple substance of Mg, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Cd, Ag, Zn, Hf, Zr, Y; Alloy such as AlSb, CuMgSb; Li-Al, Li-Al-Q (Q is 2A, 3B and/or 4B transition metal); SiB
4, SiB
6, Mg
2Si, Mg
2Sn, Ni
2Si, TiSi
2, MoSi
2, CoSi
2, NiSi
2, CaSi
2, CrSi
2, Cu
5Si, FeSi
2, MnSi
2, NbSi
2, TaSi
2, VSi
2, WSi
2, ZnSi
2, SiC, Si
3N
4, Si
2N
2O, Ge
2N
2O, SiO
t(0＜t≤2), LiSiO, LiSnO etc.
[0071] manufacture method of negative material does not have particular determination, preferred adopt raw material to be mixed by mechanical alloying method etc. be incorporated in the inert atmosphere or carry out methods of heating treatment in the reducing atmosphere.Under this situation, also the raw material more than 2 kinds can be mixed.When negative material does not contain lithium, before battery is made or after the battery making, in negative material, also can adopt the electrochemical method elements doped lithium.
[0072] negative material that adopts said method to obtain can be made the negative pole that secondary cell is used according to method commonly used in this field.For example, can be by conductive agent such as above-mentioned negative material and carbon black and binding agent be mixed, load on the negative electrode collector such as metal forming and make negative pole.As above-mentioned collector body, preferably use those not form the metal of alloy with lithium, more preferably use copper and mickel.Illustrated, also the material that can use the plating copper and mickel to form.
[0073] above-mentioned nonaqueous electrolyte does not have particular determination, for example, the nonaqueous electrolytic solution that can enumerate nonaqueous electrolytic solution by will being formed by electrolyte dissolution, solid electrolyte in non-aqueous solvent, is formed by dissolving electrolyte salt in nonaqueous solvents is impregnated into the gel-like electrolyte that forms in the matrix.
[0074] above-mentioned nonaqueous electrolytic solution can be by preparing organic solvent and the suitable combination of electrolyte.Organic solvent is so long as be applicable to this battery, just can use any, for example can enumerate, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, gamma-butyrolacton, oxolane, 2-methyltetrahydrofuran, 1,3-dioxolanes, 4-methyl isophthalic acid, 3-dioxolanes, ether, sulfolane, methyl sulfolane, acetonitrile, propionitrile, methyl phenyl ethers anisole, acetic acid esters, butyrate, propionic ester etc.
[0075],, also can use in inorganic solid electrolyte and the polymer solid electrolyte any so long as have the material of lithium ion conductive as above-mentioned solid electrolyte.As inorganic solid electrolyte, for example can enumerate lithium nitride, lithium iodide, crystalline sulfide, glass sulfide etc.Polymer solid electrolyte comprises electrolytic salt and can dissolve its macromolecular compound,, for example can enumerate ethers macromolecules such as poly-(oxirane) and crosslinked body thereof as this macromolecular compound; The methyl acrylic ester macromolecule; Homopolymers or copolymer or its mixtures such as acrylic ester high molecular type.
[0076] material of above-mentioned gel-like electrolyte matrix so long as can absorb the gelation material of nonaqueous electrolytic solution, does not just have particular determination, preferably for example can use fluorine family macromolecules such as poly-(vinylidene), poly-(biasfluoroethylene-hexafluoropropylene) copolymer; Ethers macromolecules such as poly-(oxirane) and crosslinked body thereof; Poly-macromolecules such as (acrylonitrile).Consider from the oxidation-reduction stability aspect, wish to use the fluorine family macromolecule.
[0077] given ionic conductivity owing to electrolytical existence to above-mentioned nonaqueous electrolyte.As electrolyte, so long as be applicable to this battery, just can use any, for example can use LiClO
4, LiAsF
6, LiPF
6, LiBF
4, LiB (C
6H
5)
4, CH
3SO
3Li, CF
3SO
3Li, Li (FS (=O)
2NS (=O)
2F, Li (CF
3S (=O)
2NS (=O)
2CF
3), LiCl, LiBr etc.
[0078] different with the manufacture method of lithium transition-metal silicate in the past that with the inorganic compound is the silicon supply source, the present invention uses silicon family macromolecule compound as the silicon supply source, therefore, compare with synthetic reaction in the past, can under lower temperature, synthesize, reaction control is easier, and the particle diameter of the lithium transition-metal silicate that obtains is little, and narrow particle size distribution.Therefore, use this secondary cell of the present invention that possesses the positive pole that forms by lithium transition-metal silicate, can make a kind of at the battery system that all is greatly improved aspect fail safe and stability, capacity and the cost.
[0079] the secondary cell of the present invention battery that typically can be used as coin (coin) type is made, in addition, also can make the secondary cell of various forms such as stacked type battery, bag (pack) formula battery, button (button) type battery, chewing gum (gum) formula battery, assembled battery formula battery, rectangular cell.
Embodiment
[0080] illustrate in greater detail the present invention with embodiment below, but the present invention is not limited to embodiment.
[0081] comparative example 1
According to the synthetic Li of following steps
2FeSiO
4According to stoichiometric proportion weighing Li
2CO
3(with the pure pharmaceutical worker's industry of light (strain), 99.0%), FeC
2O
42H
2O (Aldrich company, 99%), as the amorphous Si O in silicon source
2(Northeast chemistry, 99%).With putting into chromium steel container made (250ml) as the ethanol 150ml of solvent, chromium steel pearl (15mm * 10,10mm * 16), (she makes institute by rattan to use planetary ball mill with them; LP.4), carrying out pressurization in 24 hours with 240rpm mixes.Then, with tube furnace at various temperatures, sintering is 15 hours in argon gas stream.
[0082] embodiment 1
Except the silicon source is changed to phenyl polysiloxane (C
6H
5SiO
1.5)
nIn addition, all the other with the same condition of comparative example 1 under carry out Li
2FeSiO
4Synthetic.
[0083] x-ray diffraction experiment
Respectively the sample that obtains among comparative example 1 and the embodiment 1 is carried out x-ray diffraction experiment.Particularly, use by colour filter and the CoK alpha ray of monochromatization makes tube voltage, tube current be respectively 35kV, 40mA, making and measuring angle is 15 °＜2 θ＜80 °, measures under the condition of 0.028 ° of stepped intervals (stepinterval).At this moment, in mensuration, suppressed because the error effects of the caused integrated intensity of huge particle with the speed rotation of 30rpm by making sample stage.The X-ray diffraction of comparative example 1 is illustrated in Fig. 1, and the X-ray diffraction of embodiment 1 is illustrated in Fig. 2.
Find out from Fig. 1 and Fig. 2 that [0084] in comparative example 1, operate, impurity is residual many, can not get single-phase Li under the temperature below 650 ℃
2FeSiO
4, in contrast to this, in embodiment 1, can obtain single-phase Li 550 ℃ of following operations
2FeSiO
4Like this, by using (C
6H
5SiO
1.5)
nAs raw material, synthesis temperature can be reduced by 100 ℃.
[0085] electron microscope observation
Observe the Li of preparation among comparative example 1 and the embodiment 1 respectively with scanning electron microscope
2FeSiO
4Specifically, powder sample is fully pulverized in mortar, it is dispersed on the sample stage that is coated with carbon paste, measure.For fear of when observing the insulator sample, producing charging phenomenon, be to measure under the low-voltage of 1.0kV at accelerating voltage.The electron micrograph of comparative example 1 is shown in Fig. 3 (a), and the electron micrograph of embodiment 1 is shown in Fig. 3 (b).
[0086] in the observation image of comparative example 1, average grain diameter is about 70nm, and in contrast to this, in the observation image of embodiment 1, average grain diameter is about 30nm.Like this, by using (C
6H
5SiO
1.5)
nAs raw material, synthesis temperature can be reduced by 100 ℃, and suppress germination, thereby can obtain finer particle.
[0087] flash-over characteristic is measured
With the Li that obtains in the comparative example 1
2FeSiO
4As positive pole, use 2032 type button cells (coin cell) (Bao Quan (strain)), measure charge-discharge characteristic.With respect to positive active material, by weight 8: 1: 1 ratio weighings as the conductive black (ketjenblack) of conductive auxiliary agent with as Kynoar (PVDF) powder (Wu Yu chemistry (strain)) of binding agent, in solvent, add an amount of N-methyl pyrrolidone (NMP) (with the pure pharmaceutical worker's industry of light (strain)) and, make the homodisperse pastel of active material they mixing.
[0088] uses the thick aluminium foil (Niraco (strain)) of 0.1mm as the collector body of side of the positive electrode, use the doctor of 50 μ m to be coated with the pastel that contains active material.In order to make solvent evaporation, carry out drying with 120 ℃ drying machines.
[0089] through hole of getting 16mm φ on electrode peels off from collector body to avoid sample also with the pressure compacting of 50MPa.In order to improve current collection, the aluminium net of clamping 18mm φ between coating electrode and anodal jar, and suppress so that it is integrated with the pressure of 20MPa.Use is equipped with the lithium metal (this city metal (strain)) of 12mm φ through hole as negative pole, and use is equipped with the porous matter polypropylene film of 19mm φ through hole as barrier film.Use and a kind ofly in the solvent that ethylene carbonate (EC) and carbonic acid two ethyls (DEC) are mixed according to volume ratio at 7: 3, dissolve 1.0moldm
-3The LiPF as supporting electrolyte of concentration
6The solution that forms is as electrolyte.Carry out in the glove box that is produced on argon atmospher of battery.
[0090] in the charge and discharge cycles test of the battery of making, uses TOSCAT-3100 (Toyo System (strain)), under various current densities, measure.With dashed lines is shown in Fig. 4 as a result.
[0091] similarly, with the Li that obtains among the embodiment 1
2FeSiO
4As anodal, use 2032 type button cells (Bao Quan (strain)) equally, measure charge-discharge characteristic.The result is shown in Fig. 4 with solid line.Compare with comparative example 1, obtain 2～3 times discharge capacity.
[0092] comparative example 2
With the similarly synthetic Li of comparative example 1
2MnSiO
4But,, use Li as lithium source and silicon source as raw material
2SiO
3, MnC
2O
41/2H
2O, conductive black (KB) form pill by compressed mixed, in argon atmospher, under 750 ℃, and sintering 10 hours.
[0093] embodiment 2
Except the lithium source is changed to Li
2CO
3, the silicon source is changed to phenyl polysiloxane (C
6H
5SiO
1.5)
nIn addition, all the other with the same condition of comparative example 2 under carry out Li
2MnSiO
4Synthetic.
[0094] x-ray diffraction experiment
Respectively the sample that obtains among comparative example 2 and the embodiment 2 is carried out x-ray diffraction experiment.Particularly, use by colour filter and the CuK alpha ray of monochromatization makes tube voltage, tube current be respectively 50kV, 180mA, making and measuring angle is 15 °＜2 θ＜80 °, measures under the condition of 0.028 ° of stepped intervals.The results are shown in Fig. 5.(a) expression comparative example 2 among Fig. 5, (b) expression embodiment 2 among Fig. 5.
[0095] in comparative example 2, under the temperature below 750 ℃, to operate, impurity is residual many, can not get single-phase Li
2FeSiO
4, in contrast to this, in embodiment 2,, obtain single-phase basically Li 600 ℃ of operations down
2FeSiO
4Like this, by adopting (C
6H
5SiO
1.5)
nAs raw material, synthesis temperature can be reduced about 150 ℃.
[0096] electron microscope observation
Observe the Li of preparation among comparative example 2 and the embodiment 2 respectively with scanning electron microscope
2MnSiO
4Specifically, powder sample is fully pulverized in mortar, it is dispersed on the sample stage that is coated with carbon paste, measure.For fear of when observing the insulator sample, producing charging phenomenon, be to measure under the low-voltage of 1.0kV at accelerating voltage.The electron micrograph of comparative example 2 is shown in Fig. 6 (a), and the electron micrograph of embodiment 2 is shown in Fig. 6 (b).
[0097] in the observation image of comparative example 2, average grain diameter is about 80nm, and in contrast to this, in the observation image of embodiment 2, average grain diameter is about 15nm.Like this, by with (C
6H
5SiO
1.5)
nAs raw material, synthesis temperature can be reduced by 150 ℃, and suppress germination, thereby can obtain finer particle.
[0098] flash-over characteristic is measured
With the Li that obtains in the comparative example 2
2MnSiO
4As anodal, use 2032 type button cells (Bao Quan (strain)), measure charge-discharge characteristic.With respect to positive active material, by weight 8: 1: 1 ratio weighings as the conductive black of conductive auxiliary agent with as Kynoar (PVDF) powder (Wu Yu chemistry (strain)) of binding agent, in solvent, add an amount of N-methyl pyrrolidone (NMP) (with the pure pharmaceutical worker's industry of light (strain)) and, make the homodisperse pastel of active material they mixing.
[0099] uses the thick aluminium foil (Niraco (strain)) of 0.1mm as the collector body of side of the positive electrode, use the doctor of 50 μ m to be coated with the pastel that contains active material.In order to make solvent evaporation, carry out drying with 120 ℃ drying machines.
[0100] through hole of getting 16mm φ on electrode peels off from collector body to avoid sample also with the pressure compacting of 50MPa.In order to improve current collection, the aluminium net of clamping 18mm φ between coating electrode and anodal jar, and suppress so that it is integrated with the pressure of 20MPa.Use is equipped with the lithium metal (this city metal (strain)) of 12mm φ through hole as negative pole, and use is equipped with the porous matter polypropylene film of 19mm φ through hole as barrier film.Use and a kind of ethylene carbonate (EC) and carbonic acid two ethyls (DEC) are being dissolved 1.0moldm in the solvent according to 7: 3 mixed of volume ratio
-3The LiPF as supporting electrolyte of concentration
6The solution that forms is as electrolyte.Carry out in the glove box that is produced on argon atmospher of battery.
[0101] in the charge and discharge cycles test of the battery of made, uses TOSCAT-3100 (Toyo System (strain)), under various current densities, measure.The results are shown in Fig. 7.Fig. 7 (a) represents comparative example 2.
[0102] similarly, with the Li that obtains among the embodiment 2
2MnSiO
4As anodal, similarly use 2032 type button cells (Bao Quan (strain)), measure charge-discharge characteristic.The results are shown in Fig. 7.Fig. 7 (b) represents embodiment 2.
[0103] comparative example 3
With the similarly synthetic Li of comparative example 1
2CoSiO
4But,, use Li as raw material
2CO
3, CoC
2O
41/2H
2O, as the SiO in silicon source
2, form pill by compressed mixed, in air atmosphere, at various temperatures, sintering 10 hours.
[0104] embodiment 3
Except the silicon source is changed to phenyl polysiloxane (C
6H
5SiO
1.5)
nIn addition, all the other with the same condition of comparative example 3 under synthesize.
[0105] x-ray diffraction experiment
Respectively the sample that obtains among comparative example 3 and the embodiment 3 is carried out x-ray diffraction experiment.Particularly, use by colour filter and the CuK alpha ray of monochromatization makes tube voltage, tube current be respectively 35kV, 40mA, making and measuring angle is 15 °＜2 θ＜80 °, measures under the condition of 0.028 ° of stepped intervals.The results are shown in Fig. 8 and Fig. 9.Fig. 8 represents comparative example 3, and Fig. 9 represents embodiment 3.
[0106] in comparative example 3, under the temperature below 800 ℃, to operate, impurity is residual many, can not get single-phase Li
2CoSiO
4, in contrast to this, in embodiment 3,, obtain single-phase basically Li 700 ℃ of operations down
2CoSiO
4Like this, by using (C
6H
5SiO
1.5)
nAs raw material, synthesis temperature can be reduced about 100 ℃.
[0107] electron microscope observation
Observe among comparative example 3 and the embodiment 3 respectively the Li that under 700 ℃ of sintering temperatures, makes with scanning electron microscope
2CoSiO
4Specifically, powder sample is fully pulverized in mortar, it is dispersed on the sample stage that is coated with carbon paste, measure.For fear of when observing the insulator sample, producing charging phenomenon, be to measure under the low-voltage of 1.0kV at accelerating voltage.The electron micrograph of comparative example 3 is shown in Figure 10, and the electron micrograph of embodiment 3 is shown in Figure 11.
[0108] in the observation image of comparative example 3, particle diameter has the wide distribution that is about 70～300nm, and in the observation image of embodiment 3, average grain diameter is about 70nm.Like this, by using (C
6H
5SiO
1.5)
nAs raw material, synthesis temperature can be reduced about 100 ℃, and suppress germination, thereby can obtain finer particle.
[0109] flash-over characteristic is measured
With the Li by obtaining in the comparative example 3 at 800 ℃ of following sintering
2CoSiO
4As anodal, use 2032 type button cells (Bao Quan (strain)), measure charge-discharge characteristic.With respect to positive active material, by weight 8: 1: 1 ratio weighings as the conductive black of conductive auxiliary agent with as Kynoar (PVDF) powder (Wu Yu chemistry (strain)) of binding agent, in solvent, add an amount of N-methyl pyrrolidone (NMP) (with the pure pharmaceutical worker's industry of light (strain)) and, make the homodisperse pastel of active material they mixing.
[0110] uses the thick aluminium foil (Niraco (strain)) of 0.1mm as the collector body of side of the positive electrode, use the doctor of 50 μ m to be coated with the pastel that contains active material.In order to make solvent evaporation, carry out drying with 120 ℃ drying machines.
[0111] through hole of getting 16mm φ on electrode peels off from collector body to avoid sample also with the pressure compacting of 50MPa.In order to improve current collection, the aluminium net of clamping 18mm φ between coating electrode and anodal jar, and suppress so that it is integrated with the pressure of 20MPa.Use is equipped with the lithium metal (this city metal (strain)) of 12mm φ through hole as negative pole, and use is equipped with the porous matter polypropylene film of 19mm φ through hole as barrier film.Use is being dissolved 1.0moldm with ethylene carbonate (EC) and carbonic acid two ethyls (DEC) in the solvent according to volume ratio mixing in 7: 3
-3The LiPF as supporting electrolyte of concentration
6The solution that forms is as electrolyte.Carry out in the glove box that is produced on argon atmospher of battery.
[0112] in the charge and discharge cycles test of the battery of made, uses TOSCAT-3100 (Toyo System (strain)), under various current densities, measure.The results are shown in Figure 12.
[0113] similarly, with the Li that obtains at 700 ℃ of following sintering among the embodiment 3
2CoSiO
4As anodal, similarly use 2032 type button cells (Bao Quan (strain)), measure charge-discharge characteristic.The results are shown in Figure 13.
[0114] from embodiment 3 as can be seen, compare with comparative example 3, the initial stage charging capacity significantly rises to 134mAh/g from 117.9mAh/g, the initial stage discharge capacity significantly rises to 69.5mAh/g from 49.5mAh/g, increases substantially respectively.
[0115] embodiment 4
Synthetic Li
2Fe
0.5Mn
0.5SiO
4Specifically, with phenyl polysiloxane (C
6H
5SiO
1.5)
n, FeC
2O
42H
2O, MnC
2O
40.5H
2O and Li
2CO
3As raw material, add conductive black (KB) according to residual 10% condition in the end product as conductive auxiliary agent, then, pulverize mixing with planetary ball mill, in argon gas stream, under 600 ℃, carry out sintering.The powder that obtains is carried out X-ray powder diffraction measure, the result is not because at Li
2Fe
0.5Mn
0.5SiO
4Powder diffraction pattern in find the division at peak, therefore, confirm as the solid solution of Fe and Mn.In addition, use with above-mentioned same scanning electron microscope and observe, confirm that average grain diameter is about 30～40nm.
[0116] and then, measure above-mentioned synthetic Li
2Fe
0.5Mn
0.5SiO
4Charge-discharge characteristic as anodal battery.That is, according to Li
2Fe
0.5Mn
0.5SiO
4: conductive black (KB): Kynoar (PVDF)=9: 1: 1 condition of weight ratio, with Li
2Fe
0.5Mn
0.5SiO
4, KB and PVDF mix, the material that obtains as anodal, as negative pole, used lithium metal in the solvent with ethylene carbonate (EC) and carbonic acid two ethyls (DEC) mixing in 3: 7 by volume and dissolves 1.0moldm
-3The LiPF as supporting electrolyte of concentration
6The solution that forms so prepares 2032 type button cells as electrolyte, estimates its electrode characteristic.As shown in figure 14, the transition metal of per 1 atom demonstrates the 210mAhg that is equivalent to 1.27 electron reactions under 60 ℃
-1
Claims (10)
1, a kind of manufacture method, it is the manufacture method that contains the positive electrode material for secondary battery of the lithium transition-metal silicate that is expressed from the next,
[changing 1] Li
aM
bSi
cO
4
In the formula,
M is at least a kind of transition metal that is selected among Mn, Fe, Co and the Ni, and a, b and c are the number of satisfied 1＜a≤3,0.5≤b≤1.5,0.5≤c≤1.5,
It is characterized in that this method comprises following operation: will contain at least
(A) be selected from least a kind of transition metal among Mn, Fe, Co and the Ni and/or contain this transition metal metallic compound,
(B) lithium compound and
(C) silicon family macromolecule compound
Mixture sintering, obtain above-mentioned lithium transition-metal silicate.
2, the described manufacture method of claim 1 is characterized in that, carries out above-mentioned sintering under the temperature below 900 ℃.
3, the described manufacture method of claim 1 is characterized in that, lithium transition-metal silicate is the particle of average primary particle diameter less than 500nm.
4, the described manufacture method of claim 1, wherein, (A) compound that contains transition metal in the composition is at least a kind of transistion metal compound in the carbonyl-complexes of the halide of sulfate, transition metal of nitrate, the transition metal of carbonate, the transition metal of oacetic acid salt, the transition metal of acetylacetonate, the transition metal of carboxylate, the transition metal of alkoxide, the transition metal of hydroxide, the transition metal of the oxide that is selected from transition metal, transition metal and transition metal.
5, the described manufacture method of claim 1, wherein, (B) lithium compound of composition is the oxide that is selected from lithium, the hydroxide of lithium, the alkoxide of lithium, the carboxylate of lithium, the acetylacetonate of lithium, the oacetic acid salt of lithium, the carbonate of lithium, the nitrate of lithium, the sulfate of lithium and at least a kind of lithium compound in the lithium halide.
6, claim 1 or 2 described manufacture methods, wherein, (C) the silicon family macromolecule compound of composition is at least a kind of silicon family macromolecule compound that is selected from polysilane, polysilazane, polysiloxanes, Polycarbosilane and their mixture.
7, claim 1 or 2 described manufacture methods is characterized in that, (C) the silicon family macromolecule compound of composition is by repetitive:
[changing 2] C
6H
5SiO
1.5
The polyphenylene silsesquioxane of expression.
8, positive electrode material for secondary battery is by each described manufacture method manufacturing of claim 1～7.
9, anode of secondary cell comprises the described material of claim 8.
10, secondary cell possesses the described positive pole of claim 9.
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| JP2007082102 | 2007-03-27 | ||
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| JP315091/2007 | 2007-12-05 |
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| CN102315444A (en) * | 2010-07-08 | 2012-01-11 | 中国科学院宁波材料技术与工程研究所 | Nano-modified polyanionic cathode active material, preparation method thereof, and lithium ion secondary battery |
| CN102770993A (en) * | 2010-03-01 | 2012-11-07 | 古河电气工业株式会社 | Cathode active material substance, cathode, secondary battery and manufacturing methods for same |
| CN102916184A (en) * | 2012-10-23 | 2013-02-06 | 中国科学院过程工程研究所 | Lithium silicate compound of anode material of lithium ion battery, and preparation method and application for lithium silicate compound |
| CN103000890A (en) * | 2012-12-13 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cathode material Li2Mn1-x-yCoxNiySiO4 for lithium ion battery |
| CN103779559A (en) * | 2012-10-18 | 2014-05-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of lithium ion battery cathode material Li2Mn1-xMxSiO4/C |
| CN104203820A (en) * | 2012-04-16 | 2014-12-10 | 道康宁公司 | Method for preparing silicon-containing intermetallic compound and intermetallic compound prepared by same |
| CN111755670A (en) * | 2019-03-28 | 2020-10-09 | 中国科学院物理研究所 | Negative electrode material of lithium battery, preparation method and application |
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| CN102770993A (en) * | 2010-03-01 | 2012-11-07 | 古河电气工业株式会社 | Cathode active material substance, cathode, secondary battery and manufacturing methods for same |
| CN102770993B (en) * | 2010-03-01 | 2015-07-29 | 古河电气工业株式会社 | Cathode active material, positive pole, secondary cell and preparation method thereof |
| US9136535B2 (en) | 2010-03-01 | 2015-09-15 | Furukawa Electric Co., Ltd. | Cathode active material, cathode, secondary battery and manufacturing methods for the same |
| CN102315444A (en) * | 2010-07-08 | 2012-01-11 | 中国科学院宁波材料技术与工程研究所 | Nano-modified polyanionic cathode active material, preparation method thereof, and lithium ion secondary battery |
| CN102315444B (en) * | 2010-07-08 | 2016-01-20 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of nano-modified polyanionic cathode active material |
| CN104203820A (en) * | 2012-04-16 | 2014-12-10 | 道康宁公司 | Method for preparing silicon-containing intermetallic compound and intermetallic compound prepared by same |
| CN103779559A (en) * | 2012-10-18 | 2014-05-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of lithium ion battery cathode material Li2Mn1-xMxSiO4/C |
| CN103779559B (en) * | 2012-10-18 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Anode material for lithium-ion batteries Li 2mn 1-Xm xsiO 4the preparation method of/C |
| CN102916184A (en) * | 2012-10-23 | 2013-02-06 | 中国科学院过程工程研究所 | Lithium silicate compound of anode material of lithium ion battery, and preparation method and application for lithium silicate compound |
| CN102916184B (en) * | 2012-10-23 | 2016-06-08 | 中国科学院过程工程研究所 | Lithium silicate, preparation method and its usage |
| CN103000890A (en) * | 2012-12-13 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of cathode material Li2Mn1-x-yCoxNiySiO4 for lithium ion battery |
| CN111755670A (en) * | 2019-03-28 | 2020-10-09 | 中国科学院物理研究所 | Negative electrode material of lithium battery, preparation method and application |
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